Mixing-at the time of use-type hair-treating composition

ABSTRACT

A hair-treating composition having convenient usability and excellent dyeability or hair-bleachability is provided. The composition having the above excellent properties contains at least one member selected from amphoteric surface active agents or semipolar surface active agents according to circumstances, and cationic polymers, in combination with an anionic surface active agent and a higher fatty acid, and further contains a dye or an alkalinizing agent.

TECHNICAL FIELD

This invention relates to a mixing-at the time of use-type hair-treatingcomposition. More specifically, the invention relates to a hair dyecomposition and a hair-bleaching agent composition each containingparticular components in such a state that they are combined.

BACKGROUND ART

Heretofore, as mixing-at the time of use-type (namely, two or moreagents are combined at the time of use) hair-treating compositions,particularly hair dyes and hair-bleaching agents, twin pack ones haveusually been used, and a typical hair-treating composition is one formedby mixing the first agent containing as a principal agent an oxidationdye including an aromatic amino compound and/or an alkalinizing agentsuch as ammonia with the second agent containing as a principal agent anoxidizing agent such as hydrogen peroxide at the time of use. Thismixture is applied onto hair at the time of use, and therefore themixture is required to have a viscosity of such a degree that it doesnot drip from the hair. Thus in prior art, a thickening system at thetime of mixing has been obtained by utilizing the crystalline region ofan aqueous nonionic surface active agent solution. Namely, a. thickeningsystem has been obtained by diluting the first agent wherein a thicknonionic surface active agent having a concentration equal to or higherthan the liquid crystal formation concentration and a lower alcohol arecompounded together with a dye or an alkalinizing agent, with the secondagent containing an oxidizing agent to adjust the concentration of thesurface active agent in the final mixture to its liquid crystal region.However, particularly as to dyeing agents, usual systems whereinnonionic surface active agents and lower alcohols are thick haddrawbacks that the hair after dyeing is dry to the touch, and since itbecomes liquid crystals at the time of mixing, dispersion of the dye isbad and its dyeability is bad.

On the other hand, for the purpose of providing a hair dye making dyeingof hair or giving it a color tone, and at the same time washing andconditioning possible, a hair dye is proposed which contains a cationicpolymer, an anionic surface active agent, and an amphoteric oramphoteric ionic surface active agent, in specific rates, respectively(for example, see Japanese Patent Publication No. 22884/1992).

However, it has been difficult to stably provide such a hair dye orhair-bleaching agent that in the preparation compositions before mixingin a separated form, they are stable in physical properties and exhibitrelatively low viscosities, but at the time of use, namely when all thecomponents are mixed, the mixed composition does not drip from the hair,and that it is excellent in desired dyeing or decolorization, and thetouch of the hair after deying or decolorization, etc.

For example, as to the above composition wherein a lower alcohol wasused, there was a tendency that the touch of hair after such treatmentis poor.

Thus, the object of the invention lies in providing such a mixing-at thetime of use-type hair-treating composition that from a composition atthe time of use wherein respective components are mixed, part or all ofthe lower alcohol can be removed, and moreover when the respectivecomponents are independent with one another or in such a form that theyare separated as certain groups, they relatively exhibit lowviscosities, but when the respective components are combined to be in amixed state, the mixture exhibits a moderate viscosity.

DISCLOSURE OF INVENTION

It is known that although it does not belong to the technical field ofhair dyes, a composition containing an anionic surface active agent, anamphoteric surface active agent and/or a semipolar surface active agent,and a higher fatty acid has, as a skinwashing agent, a moderateviscosity (For example, see Japanese Laid-open Patent Publication No.17342/1993 and Japanese Laid-open Patent Publication No. 65596/1994).

The present inventors found that as to the respective components of sucha composition, when they are subjected to preparation, together with adye and a peroxide as essential components of a mixing-at the time ofuse-type hair dye, respectively alone or in specific combinations, theresultant respective preparations are stable and have relatively lowviscosities, but when all of them are mixed, a mixed composition can beprovided which exhibits an excessive viscosity for the purpose of use asa hair dye.

Thus, the above object can be attained by providing a mixing-at the timeof use-type hair-treating composition, particularly hair dye orhair-bleaching agent composition, by the invention, wherein a dye oralkalinizing agent and an oxidizing agent are combined at the time ofuse, wherein

(a) the composition after the combination comprises a dye (I) or analkalinizing agent (I'), one or more (II) of surface active agentsselected from the group consisting of amphoteric surface active agentsand semipolar surface active agents, (II) being optional components),one or more (III) of higher fatty acids, one or more (IV) of anionicsurface active agents, an oxidizing agent (V), and water (VII), and

(b) before use, components selected from the group consisting ofcomponent (I) or the alkalinizing agent (I'), components (II) and (III)are put in such a form that they are separated from component (V).

Further, according to the invention, there is provided a compositioncontaining cationic polymer(s) (VI) as additional component(s), namely amixing-at the time of use-type hair-treating composition, particularlyhair dye or hair-bleaching agent composition wherein a dye oralkalinizing agent and an oxidizing agent are combined at the time ofuse, wherein

(a) the composition after the combination comprises a dye (I) or analkalinizing agent (I'), one or more (II) of surface active agentsselected from the group consisting of amphoteric surface active agentsand semipolar surface active agents, (II) being optional component(s),one or more (III) of higher fatty acids, one or more (IV) of anionicsurface active agents, an oxidizing agent (V), a cationic polymer (VI)and water (VII), and

(b) before use, components selected from the group consisting ofcomponent (I) or (I'), (II) and (III) and (IV) are put in such a formthat they are separated from components selected from the groupconsisting of components (V) and (VI).

BEST MODE OF CARRYING OUT THE INVENTION

The term of "mixing-at the time of use-type" used in the invention meanssuch a style that previously prepared, two or more preparations aremixed at the time of use, namely at the time of hair treatment. Thus,the invention is, generally, convenient for application to such a hairdye as called a permanent hair dye, but it can also be applied to ahair-bleaching agent by substituting an alkalinizing agent for the dye.

Therefore, although, for making it concise, the following description ismade mainly on application to hair dyes, it should be understood thatthe description becomes that for hair-bleaching agents by substitutingalkalinizing agents for the dyes.

As dyes (component (I)) used in the invention, there can be mentioneddye precursors coloring by oxidation of the compounds themselves, andcombinations of a dye precursor with a coupler giving various colortones by combination with the dye precursor. Although not limitedthereto, as specific examples of such dyes, there can be mentioned5-aminoorthocresol (another name paraaminoorthocresol),2-amino-4-nitrophenol, 2-amino-5-nitrophenol,1-amino-4-methylaminoanthraquinone, 3,3'-iminodiphenol,2,4-diaminophenol hydrochloride, toluene-2,5-diamine hydrochloride,nitroparaphenylenediamine hydrochloride, paraphenylenediaminehydrochloride, N-phenylparaphenylenediamine hydrochloride,metaphenylenediamine hydrochloride, orthoaminophenol,N-phenylparaphenylenediamine acetate, 1,4-diaminoanthraquinone,2,6-diaminopyridine, diphenylamine, toluene-2,5-diamine,toluene-3,4-diamine, nitroparaphenylenediamine, paraaminophenylsulfamicacid, paraaminophenol, paranitroorthophenylenediamine,paraphenylenediamine, paramethylaminophenol,N,N'-bis(4aminophenyl)-2,5-diamino-1,4-quinonediimine (another nameBandrofsky base), sodium2-hydroxy-5-nitro-2',4'-diaminoazobenzene-5-sulfonate (another nameChrome Brown RH), N-phenylparaphenylenediamine, metaaminophenol,metaphenylenediamine, 5-aminoorthocresol sulfate (another nameparaaminoorthocresol sulfate), 2-amino-5-nitrophenol sulfate,4,4'-diaminodiphenylamine sulfate, toluene-2,5-diamine sulfate,nitroparaphenylenediamine sulfate, paraaminophenol sulfate,paranitroorthophenylenediamine sulfate, paranitrometaphenylenediaminesulfate, paraphenylenediamine sulfate, paramethylaminophenol sulfate,metaaminophenol sulfate, metaphenylenediamine sulfate, and/or hemateincalled a vegetable dye, tannic acid and aromatic polyhydric alcoholssuch as catechol and resorcinol

The above dyes are appropriately used in accordance with desired dyeingcolor, and in some case, they can be used in combination. Thecompounding amount of the dye is usually 0.001 to 10 weight %,preferably 0.01 to 5 weight %.

In the hair-bleaching agent composition, at least one of variousinorganic and organic alkalis can be used as an alkalinizing agent(component (I')), in place of the above dye. These alkalinizing agentscan appropriately be used in accordance with desired bleaching effect,and can be used so as to make the system a pH of 6 to 12.

On the other hand, as the oxidizing agent (component (V)), any one canbe used so long as it is such a compound or system that when contactedwith the above oxidation dye, it acts so as to bring about coloringbased on the dye, and in the hair-bleaching agent composition, whencontacted with an alkalinizing agent, it acts so as to bring aboutbleaching of hair, and the object of the invention is not badlyinfluenced. Usually, it is preferred to use hydrogen peroxide as such acompound. Further, as the above system, there can be used anoxidation-reduction system wherein hydrogen peroxide and ammoniumpersulfate or another persulfate are combined or an oxidation-reductionsystem wherein hydrogen peroxide and sodium pyrosulfite are combined,which acts so as to accelerate bleaching (or) decolorization of hair aswell as coloring of the dye. In such a system, hydrogen peroxide is putbefore use in such a form that it is separated from another peroxide,etc.

The use amount of the oxidizing agent cannot be limited because itsoptimum amount is varied depending on the kind of dyes used, the kind ofeach component constituting the mixed composition at the time of use andthe pH, but when hydrogen peroxide is used, it is preferred to selectthe use amount so as to be generally 0.2 to 20 weight %, preferably 1 to5 weight % based on the whole weight of the composition.

In the invention, as to amphoteric surface active agents (component(II)) optionally used, any ones can be used so long as they areamphoteric surface active agents used in usual cosmetic bases, etc. Asspecific examples thereof, there can be mentioned amidobetaine-typeamphoteric surface active agents represented by the general formula (A)##STR1## as products on the market, Revon 2000 (produced by Sanyo KaseiCo.), Anon BDF (produced by Nippon Oil & Fats Co.), etc. are referredto!,

amidosulfobetaine-type amphoteric surface active agents represented bythe general formula (B) ##STR2## as products on the market, Ronzaine-CS(Produced by Ronza Co.), Miratine CBS (Produced by Miranol Co.), etc.are referred to!,

betaine-type amphoteric surface active agents represented by the generalformula (C) ##STR3## as products on the market, Anon BL (produced byNippon Oil & Fats Co.), Dehynton AB-30 (produced by Henkel Co.), etc.are referred to!,

sulfobetaine-type amphoteric surface active agents represented by thegeneral formula (D) ##STR4## as products on the market, Ronzaine-12CS(Produced by Ronza Co.), etc. are referred to!,

imidazolinium-type amphoteric surface active agents represented by thegeneral formula (E) ##STR5## as products on the market, Ovazoline 662-N(Produced by Toho Chemical Industry Co.), Anon GLM (Produced by NipponOil & Fats Co.), etc. are referred to!, etc.

Further, as semipolar surface active agents (component (II)) optionallyused, there can be exemplified tertiary amine oxide-type semipolarsurface active agents represented by the general formula (F) ##STR6## asproducts on the market, Unisafe A-LM (Produced by Nippon Oil & FatsCo.), Wandamin OX-100 (Produced by Shinnippon Rika Co.), etc. arereferred to!, etc.

In this connection, in the general formulae (A) to (F), R₁ is preferablyan al kyl group or al kenyl group having on average 9 to 21 carbonatoms, more preferably an alkyl group or alkenyl group having on average11 to 17 carbon atoms, most preferably an alkyl group or alkenyl grouphaving on average 11 to 13 carbon atoms. When the average carbon numberis under 9, hydrophilic properties are stronger compared with the caseof 9 or more, and there is a tendency that the thickening action offinal products becomes lower. On the other hand, when it exceeds 21,solubility into water becomes bad compared with the case of 21or less,and there is a tendency that the phase separation of these componentsoccurs in the final mixture composition or in preparations before usecontaining these components, and thus the stability of the compositionsbecomes bad.

R₂ represents an alkyl group or alkenyl group having on average 10 to 18carbon atoms. x is an integer of 2 to 4, y is an integer of 0 to 3, andz is an integer of 1 or 2.

In the invention, any one or two or more of these amphoteric surfaceactive agents and semipolar surface active agents can be selected andused. As preferred ones among combinations of two or more, there can bementioned combinations of imidazoliniumbetaine-type amphoteric surfaceactive agent(s) with at least one of other types.

Specifically, it is preferred to use combinations of at least one ofimidazoliniumbetaine-type amphoteric surface active agents with at leastone selected from the group consisting of amidobetaine-type amphotericsurface active agents, amidosulfobetaine-type amphoteric surface activeagents, sulfobetaine-type amphoteric surface active agents and tertiaryamine oxide-type semipolar surface active agents.

As stated later, there is a case where when a specific kind of anionicsurface active agents used in combination is selected, it is not alwaysnecessary to incorporate the above components in the hair-treatingcomposition of the invention.

As higher fatty acids (component (III)) used in the invention, any onescan be used so long as they are higher fatty acids, for example,represented by the following general formula (G), and being used inusual cosmetic bases, etc. General formula (G)

    R.sub.3 COOH                                               (G)

Herein, R₃ is preferably a saturated or unsaturated hydrocarbon having astraight chain or branched chain having on average 7 to 25 carbon atomsor a mercury group, more preferably a saturated or unsaturatedhydrocarbon having a straight chain or branched chain having on average9 to 23 carbon atoms or a hydroxyl group, most preferably a saturated orunsaturated hydrocarbon having a straight chain or branched chain havingon average 11 to 21 carbon atoms or a hydroxyl group. When the averagecarbon number is under 7, thickening action at the time of mixing isweak compared with the cases of 7 or more. On the other hand, when itexceeds 25, the solubility in the first agent is small, phase separationoccurs and the system becomes highly viscous, compared with the cases of25 or more.

As specific examples of higher fatty acids, there can be mentionedsaturated fatty acids such as lauric acid, myristic acid, palmitic acid,stearic acid, arachic acid and behenic acid; unsaturated fatty acidssuch as 2-palmitoleic acid, petroselinic acid, oleic acid, elaidic acid,ricinolic acid, linolic acid, linoelaidic acid, linolenic acid andarachidonic acid; branched fatty acids such as isostearic acid;hydroxycarboxylic acids such as 12-hydroxystearic acid; etc. Among them,in view of stability and stimulus properties on skin, saturated fattyacids having 18 carbon atoms, particularly ones having a branch arepreferred, and fatty acids which are liquid at room temperature, forexample, a saturated fatty acid having 18 carbon atoms and a methylbranch and oleic acid are more preferred. As products on the market,there can, for example, be mentioned isostearic acid (Emery #871 and#875 (produced by Emery Co.), oleic acid (Extraolein 90 and 99 (producedby Nippon Oil & Fats Co.), etc.

Although the invention is not limited by action mechanism, when such ahigher fatty acid is used in combination with the above component (I),the component (II) as an optional component and a later-describedanionic surface active agent, the stability at low temperatures of aprepared composition (generally, the first agent) containing them isremarkably heightened, and moreover, the viscosity of the mixedcomposition at the time of use is significantly heightened.

In the invention, among the above higher fatty acids, any one or twoones are selected and used.

The viscosity of the mixed composition at the time of use is increasedas the compounding amount of the higher fatty acid is increased, and,particularly, it is preferred to compound the higher fatty acid in anamount of 0.1 to 5 weight %.

When higher fatty acids being liquid at room temperature such asisostearic acid and oleic acid are used, the above effects are stillfurther increased, and compositions prepared using them were stable evenat low temperatures of -5° C. or less.

As anionic surface active agents (component (IV)) usable in theinvention, there can, for example, be mentioned fatty acid soaps such asbases for soaps, sodium laurate and sodium palmitate, higher alkylsulfate ester salts such as sodium lauryl sulfate and potassium laurylsulfate, POE alkyl ether sulfates such as triethanolammonium POE laurylsulfate and sodium POE lauryl sulfate, N-acylsarcosine acids such assodium lauroylsarcosinate, alkyloylalkyltaurine salts such as sodiumN-myristoyl-N-methyltaurate and sodium N-lauroyl-N-methyltaurate, higherfatty acid amidosulfonate salts such as sodium cocoylmethyltaurate andsodium laurylmethyltaurate, phosphate ester salts such as sodium POEoleyl ether phosphate and POE stearyl ether phosphate, sulfosuccinatesalts such as sodium di-2-ethylhexylsulfosuccinate, sodiummonolauroylmonoethanolamidopolyoxyethylenesulfosuccinate and sodiumlaurylpolypropyleneglycolsulfosuccinate, alkylbenzenesulfonate saltssuch as sodium linear dodecylbenzenesulfonate, triethanolammonium lineardodecylbenzenesulfonate and linear dodecylbenzenesulfonic acid,N-acylglutamate salts such as monosodium N-lauroyl-glutamate, disodiumN-stearoylglutamate and monosodium N-myristoyl-L-glutamate, higher fattyacid ester sulfate ester salts such as sodium hardened coconut oil fattyacid glycerol sulfate, sulfated oils such as Turkey red oil, POE alkylether carboxylates, POE alkyl allyl ether carboxylate salts,α-olefinsulfonate salts, higher fatty acid ester sulfonate salts,secondary alcohol sulfate ester salts, higher fatty acid alkylol amidesulfate ester salts, sodium lauroylmonoethanolamidosuccinate,ditriethanolamine N-palmitoylaspartate, casein sodium, etc.

In this connection, "POE" in the above exemplification meanspolyoxyethylene, and includes ones wherein the ethylene oxide unit isusually 1 to 20.

Among them, those particularly conveniently usable for heightening theviscosity of the mixed composition at the time of use are POE alkylether sulfate salts such as sodium POE lauryl sulfate,triethanolammonium POE lauryl sulfate, triethanolammonium POE myristylsulfate and sodium POE myristyl sulfate, and alkyloyl-alkyltaurine saltssuch as N-lauroyl-N-methyltaurine salts and N-myristyl-N-methyltaurinesalts, wherein the carbon number of the alkyl chain is any even numberin the range of 10 to 18, and further α-olefin sulfonate salts.

When these conveniently usable ones are contained in the hair-treatingcomposition of the invention, the desired objects can be attainedwithout using component (II) together. According to the invention, as tothese anionic surface active agents, one or more of them can be used inappropriate combinations, and in preparations before use, they can, forexample, be mixed with a dye or an alkalinizing agent, or mixed with anoxidizing agent. Thus, they can be used in such a form that they aremixed with component (II) and component (III) or separated therefrom. Inthis separated form, a preparation before use can be prepared in such aform that component (IV) is mixed with with an oxidizing agent (V), or asmall amount of it is used in combination with component (II) andcomponent (III) and a greater amount of it is put in such a form that itis separated from component (II) and component (III).

As cationic polymers (component (VI)) used as an additive component inthe invention, all of cationic polymers used in usual cosmetic bases,etc. can be adopted. As specific examples thereof, there can beexemplified

quaternary nitrogen-containing cellulose ether derivatives representedby the general formula (H): ##STR7## (as products on the market, PolymerJR-400, JR-30M and JR125 (produced by Union Carbide Co.), etc. arereferred to),

diallyldimethylammonium salt-acrylamide copolymers represented by thegeneral formula (I): ##STR8## (as products on the market, Marcoat 550(produced by Merck & Co. and Calgon Co.), etc. are referred to), and

poly(diallyldimethylammonium salt) derivatives represented by thegeneral formula (J): ##STR9## (as products on the market, Marcoat 100(produced by Merck & Co. and Calgon Co.), etc. are referred to).

As specific examples of the cationic polymer (component (VI)), there canfurther, for example, be exemplified a cationic copolymer obtained bypolymerizing a monomer composition for thickeners containing

15 to 90 weight % of an amine-containing (meth)acrylic monomerrepresented by the general formula (K): ##STR10## (wherein, R¹represents a hydrogen atom or a methyl group, R² and R³ eachindependently represent a hydrogen atom, a methyl group, an ethyl groupor a tert-butyl group, A represents an oxygen atom or an --NH-- group,and B represents an alkylene group of 1 to 4 carbon atoms which isstraight-chain or has a side chain),

0 to 80 weight % of a vinyl monomer represented by the general formula(L): ##STR11## (wherein, R¹ is as defined above, and R⁴ represents agroup represented by the general formula: ##STR12## (wherein, prepresents 3 or 4) or a group represented by the formula: ##STR13## 1 to60 weight % of a (meta)acryloyl group-containing monomer represented bythe general formula (M): ##STR14## (wherein, R¹ and A are as definedabove, R⁵ represents an alkylene group of 1 to 17 carbon atoms which isstraight-chain or has a side chain, or a group represented by thegeneral formula (N): ##STR15## (wherein, n represents an integer of 1 to4, and q represents an integer of 1 to 25), and R⁶ represents a hydrogenatom or a methyl group), and 0.1 to 25 weight % of a crosslinkable vinylmonomer.

In the invention, among the above cationic polymers, any one or two ormore of them are selected and used.

Although thickening effect at the time of mixing is heightened as thecompounding amount of the cationic polymer is increased, when thecompounding exceeding 5% was made at the time of mixing, the thickeningeffect is, conversely, lowered. The compounding amount is preferably0.01 to 5%, and when the thickening effect is taken into account, it isparticularly preferably 0.1 to 1%.

When the cationic polymer is used, in view of properties of the peroxide(component (V)) and the cationic polymer (component (VI)), it isdesirable in preparations before use of the invention to avoid use incombination of component (I), component (II) as an optional componentand component (III) with component (V) and component (VI). Thus, as tothe hair dye composition of the invention which is subjected to mixingat the time of mixing, supposing that it is composed of two agents, itis convenient for handling to provide it as a two-agent-type compositionwherein the first agent is prepared from component (I), component (II),component (III), component (IV) and water (component VII), and thesecond agent is prepared from component (V), component (VI) andcomponent (VII).

When a composition at the time of use wherein the respective componentsare combined and mixed is made to contain, based on the total amount ofthe components, 5 to 50 weight % of components (IV) and (II), 0.1 to 5weight % of component (III), and if necessary, 0.01 to 5 weight % ofcomponent (VI) as an additional component, it is possible to maintainthe viscosity of the preparations before use (for example, the abovefirst agent and the second agent) relatively low (usually, 200 cps orless), and nevertheless it is possible to make the viscosity of themixed composition at the time of use significantly higher (generally 500to 10,000 cps, preferably 500 to 5,000 cps, more preferably 1,000 to3,000 cps). In this connection, the above viscosity means a valuemeasured at 30° C. When the total amount of components (IV) and (II) isunder 5%, it is impossible to sufficiently heighten the viscosity of themixed composition at the time of use, and when the total amount thereofexceeds 50%, the system of the mixed composition comes to exhibit suchbehavior that liquid crystals are formed, which is not desired.

Further, the weight ratio at the time of mixing of the anionic surfaceactive agent (component (IV)) to the amphoteric surface active agentand/or semipolar surface active agent (component (II)) can be selectedso as to be 4/6 to 10/0. In this weight ratio range, high thickeningeffect can be obtained in a broader pH range (specifically pH 6 to 12)at the time of mixing of the above first agent and the second agent, andthus a hair dye having high dyeability and high uniformity of dyeing ongray or white hair can be obtained. Further, it also becomes possible todye hair to bright color so-called dressing up dyeing. Particularly, thehair dye is fit for dyeing of gray or white hair at a pH of 6 or moreand under 8, and for dressing up dyeing at a pH of 8 to 12. The firstagent and the second agent, and their mixture each exhibit desirableviscosity and stability. It is more desirable to adjust the weight ratioof component (IV)/component (II) to 4/6 to 6/4.

According to the invention, in addition to the above combinations of therespective components, it is also important to make adjustment so thatthe mixed composition at the time of use can have a pH of 6 to 12. Bysuch adjustment of pH, it becomes possible to maintain the viscosity ofthe mixed composition (namely, the hair dye composition at the time ofuse) moderately and moreover heighten dyeing characteristics.

As stated above, according to the invention, when the additionalcomponent (VI) is made to be contained a preparation comprising acombination of, at least, component (I) or component (I'), component(II) as an optional component, component (III) and component (VII) isput, before use, in such a form that it is separated from a preparationcomprising a combination of component (V), component (VI) and component(VII). Also in this case, it is suitable that the same pH range and useamount of component (IV) and component (II) as in the mixed compositionnot containing the above component (VI) are adopted.

For making the first agent alkaline, an alkaline pH adjusting agent iscompounded. As specific examples of the pH adjusting agent, there can,usually, be mentioned ammonia water, alkanolamines such asmonoethanolamine, hydroxides such as sodium hydroxide and potassiumhydroxide, carbonates such as sodium carbonate, and silicates such assodium silicate. Further, there can also be used inorganic ammoniumsalts such as ammonium sulfate, ammonium nitrate, ammonium chloride,ammonium bicarbonate, ammonium dihydrogenphosphate and diammoniumhydrogenphosphate. Further, these can also be used as as a constituentof the alkalinizing agent when the composition of the invention is madeas a hair-bleaching agent.

The pH at the time of use of the hair-treating composition of theinvention can be adjusted either by compounding a pH adjusting agentbefore mixing of the first agent with the second agent, or by adding itat the time of mixing. In this connection, "at the time of mixing" meansduring mixing or after mixing, but it is preferred to make thecompounding during the mixing.

Further, in the hair-treating composition of the invention, it is alsopossible to compound a lower alcohol in such a range that the effects ofthe invention are not influenced (namely, preferably in an amount of 3weight % or less in the first agent). As specific examples of the loweralcohol, there can usually be mentioned monohydric alcohols having 2 to5 carbon atoms such as ethyl alcohol, n-propanol, isopropanol andbutanol. In hair dyes, by incorporating a lower alcohol, permeation ofthe dye into hair is accelerated, but the touch of the hair is loweredthereby, and thus there is often a case where it is preferred not tocompound it. On the other hand, since in usual hair dyes, a large amountof a lower alcohol is compounded in the first agent, but in theinvention, its content can be made zero or small, the hair dye of theinvention can be one excellent in use feeling even at the time ofrinsing.

Other hair-protecting agents, stabilizers, perfumes, humectants, etc.can be incorporated into the hair-treating composition of the invention,at the stage of preparations therefor or at the stage of thepreparations having been mixed, in such a range that the objects of theinvention are not spoiled.

As stated above, the hair-treating composition of the inventionincluding both of the preparations before use and the combination ofthese preparations at the time of use, when the final product wasapplied to hair, exhibits excellent dyeing characteristics as a hairdye, without substantially bringing about dropping from the hair.Further, each preparation is excellent in preservation stability andcovenient for handling, and further can be provided as a compositionhaving a relatively low viscosity.

The invention is further described below according to specific examples.Parts or percentages (%) used in the examples mean (weight/weight) partsor (weight/weight) % unless otherwise defined.

First, methods for evaluating the effects of the invention are shown.

1) Dyeability test using hair strands

Hair strands (2 g) previously bleach (decolorization)-treated werecoated with 10 g of a hair dye, and evaluation was made based on therelations between time for which the hair strands were left alone andthe L value. In this connection, the L value means the value of L in thecolor difference equation of Hunter.

2) Comparative test on dyeability and dryness to the touch by a panel ofexperts

A series of hair dyeing operations was conducted, and dyeability of thehair and dryness to the touch after drying were evaluated according tothe following criterion, using a panel of 10 experts. <Dyeability>

++ . . . Dyeability is remarkably good and the hair is uniformly dyed

+ . . . Dyeability is good and the hair is uniformly dyed

± . . . Dyeability is a little poor

- . . . The hair is unevenly dyed and there is no dyeability

<Dryness to the touch>

++ . . . The hair is not dry to the touch and gives smooth touch

+ . . . The hair is not dry to the touch

± . . . The hair is a little dry to the touch

- . . . The hair is strikingly dry to the touch

3) Viscosity of mixed solution

The first agent and the second agent were mixed and the viscosity of themixed solution was measured at 30° C. using a Brook-field typeviscometer.

4) Low temperature stability

The first agent (100 g) was stored in a constant temperature bath of -5°C. for one month, and the state thereof was visually observed andevaluated according to the following criterion.

++ . . . Any change is not observed at all compared with the initialstate

+ . . . Any change is not observed at all compared with the initialstate, but there is a slight increase of the viscosity

± . . . A slight turbidity is formed

- . . . Separation occurs

EXAMPLE 1 AND COMPARATIVE EXAMPLE 1 (USUAL SYSTEM)

In the following example, the effects of the composition of theinvention in the case where an anionic surface active agent is used inmixing with an oxidizing agent are illustrated.

The following first agent and the second agent of the invention or ausual system were mixed in a ratio of 1:1 to prepare a hair dye, andusing hair strands, the difference in dyeability between the inventionand the usual system was evaluated based on relations between time forwhich the hair strands were left alone and the L value.

Further, the viscosities of the first agent and the second agent, andthe viscosity after mixing of both were measured.

Example 1

    ______________________________________                                                           (weight %)                                                 ______________________________________                                        (The first agent)                                                             Undecyl-N-hydroxyethyl-N-                                                                          3.0                                                      carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                7.0                                                      Oleic acid           3.0                                                      Monoethanolamine     2.0                                                      Ammonia water (28%)  10.0                                                     L-ascorbic acid      0.5                                                      Paraphenylenediamine 1.0                                                      Resorcinol           1.0                                                      Perfume              Appropriate amount                                       Purified water       Balance                                                  Total                100.0                                                    (The second agent)                                                            Sodium Polyoxyethylene (1.5) alkyl                                                                 10.0                                                     (12, 14) ether sulfate                                                        Aqueous hydrogen peroxide                                                                          20.0                                                     Methylparaben        Appropriate amount                                       Sodium stannate      Appropriate amount                                       Phosphate buffer     Adjusted to pH 3                                         Purified water       Balance                                                  Total                100.0                                                    ______________________________________                                    

Comparative Example 1

    ______________________________________                                        (The first agent)                                                             Polyoxyethylene (2) oleyl ether                                                                    15.0                                                     Polyoxyethylene (5) octylphenyl ether                                                              5.0                                                      Oleic acid           10.0                                                     Monoethanolamine     2.0                                                      Ammonia water (28%)  10.0                                                     Paraphenylenediamine 1.0                                                      Resorcinol           1.0                                                      L-ascorbic acid      0.5                                                      Sodium hydrosulfite  0.1                                                      Perfume              Appropriate amount                                       Purified water       Balance                                                  Total                100.0                                                    (The second agent)                                                            Aqueous hydrogen peroxide (30%)                                                                    20.0                                                     Methylparaben        Appropriate amount                                       Sodium stannate      Appropriate amount                                       Phosphate buffer     Adjusted to pH 3                                         Purified water       Balance                                                  Total                100.0                                                    ______________________________________                                    

The L value at 20 minutes after the treatment with the hair dye ofExample 1 was 14.6 and that in the case of the comparative example was16.9, and also by visual observation, the product of the invention wassuperior to the usual system in dyeability.

Next, the dyed hair was irradiated with carbon arc for 20 hours or witha xenon lamp for 30 hours, and change of L values (ΔL) was checked. InComparative example 1, ΔL was 12.2 (xenon), whereas in the presentexample, ΔL was 3.6 (xenon), and the hair dyed with the present examplewas found to be slow to discolor.

Further, as to the first agent of Example 1, the pH was 10.65 and theviscosity was 150 cps, and as to the second agent, the pH was 3.0 andthe viscosity was 12 cps, and after both were mixed, the pH became 9.3and the viscosity became 4,200 cps, and remarkable thickening effect wasobserved.

Next, the first agent and the second agent of Example 1 were used, andan appropriate amount of a pH-adjusting agent (ammonia water orphosphoric acid) was added at the time of mixing to prepare hair dyes ofpH 5, 6 and 12, respectively. When viscosity was measured, theviscosities of these hair dyes were 460 cps, 2,510 cps and 890 cps,respectively, and it was found that in hair dyes of the inventionwherein the pH is 6 to 12, excellent thickening effect can be obtained.Further, the L values at 20 minutes after the hair dyeing treatment were52, 23 and 38, respectively, and it was revealed that dyeability is highin the range of pH 6 to 12.

Examples 2 to 25 and Comparative Examples 2 to 9

Evaluation was made according to the above evaluation method on hairdyes obtained by mixing the first agents and the second agents eachhaving various compositions. The results are shown together in Tables 1to 4 . In the following tables, the expression "to 100" means purifiedwater is added upto 100 weight %.

                                      TABLE 1                                     __________________________________________________________________________                     Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    2    3    4    5    6    7    8    9                         __________________________________________________________________________    (The first agent)                                                             Undecyl-N-hydroxy-N-carboxy-                                                                   8    --   2    3    4    8    15   4                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            --   --   8    12   --   7    3      2.66                    Sodium Lauroamphoacetate                                                                       --   --   --   --   6    --   --   --                        Oleic acid       2    3    3    3    3    3    4    2                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   --                        product)                                                                      Monoethanolamine 1    2    2    2    2    2    2    1                         Ammonia water (28%)                                                                            10   15   10   15   10   15   15   10                        L-ascorbic acid    0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                     Sodium hydrosulfite                                                                            --     0.1                                                                              --   --     0.1                                                                              --     0.1                                                                              --                        Paraphenylenediamine                                                                           1    1      0.5                                                                              1    1    1      1.5                                                                                0.8                     Resorcinol       --   1      0.2                                                                                0.5                                                                                0.5                                                                              1      0.8                                                                                0.4                     Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            Triethanolammonium polyoxyethylene                                                             8    10   15   10   10   10   9    15                        (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       --   --   --   --   --   --   --   --                        Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   --   --   --                        O- 2-hydroxy-3-(trimethylammonio)-                                                             --   --   --   --   --   --   --   --                        propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                  --   --   --   --   --   --   --   --                        polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --   --   --   --   --   --                        acrylamide copolymer                                                          Vinylpyrrolidone-N,N-                                                                          --   --   --   --   --   --   --   --                        dimethylaminoethyl methacrylate-                                              stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1    1/1.5                                                                            1/2  1.5/1                     second agent)                                                                 Weight ratio (anionic surface active                                                           5/5  10/0 6/4  4/6  5/5  5/5  5/5  4/6                       agent/amphoteric surface active agent)                                        pH at the time of mixing                                                                         9.5                                                                                9.8                                                                                9.2                                                                                9.5                                                                                9.2                                                                                9.2                                                                              9      9.4                     Dyeability       ++   ++   ++   ++   ++   ++   ++   ++                        Dryness to the touch                                                                           ++   ++   ++   ++   ++   ++   ++   ++                        Viscosity of the first agent                                                                   100  120  110  150  130  130  150  110                       Viscosity of the second agent                                                                  40   40   40   55   45   50   40   40                        Viscosity after mixing                                                                         3000 2500 5000 2800 3800 1900 2300 1500                      Low temperature stability                                                                      ++   ++   ++   ++   ++   ++   ++   ++                        __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________                     Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    10   11   12   13   14   15   16   17                        __________________________________________________________________________    (The first agent)                                                             Undecyl-N-hydroxy-N-carboxy-                                                                   2    1    2    2    2    5    4    6                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            6    9    6    4    10   10   6    6                         Sodium Lauroamphoacetate                                                                       --   --   --   2    --   --   --   --                        Oleic acid       2    3    3    3    3    3    3    2                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   1                         product)                                                                      Monoethanolamine 1    2    2    2    2    2      2.5                                                                              3                         Ammonia water (28%)                                                                            10   10   10   10   12   10   --   --                        L-ascorbic acid    0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                     Paraphenylenediamine                                                                           1    1      0.5                                                                              1    1    1    1    1                         Resorcinol       --   1    1    1    1    1      0.5                                                                              1                         1,3-Butylene glycol                                                                            2    1    3    2      1.5                                                                              2      4.5                                                                              4                         Ethanol          --   --   --   --   --   2    --   --                        Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            Triethanolammonium polyoxyethylene                                                             8    10   10   --   --   --   5    5                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       --   --   2    8    8    10   --   3                         Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   --   5    --                        O- 2-hydroxy-3-(trimethylammonio)-                                                             --   --     0.5                                                                              --   --   --   --   --                        propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                    0.5                                                                              --   --   --   --   --   --   --                        polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --     0.3                                                                              --   --   --   --                        acrylamide copolymer                                                          Vinyl pyrrolidone-N,N-                                                                         --   --   --   --   --   --     0.5                                                                              --                        dimethylaminoethyl methacrylate-                                              stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1    1/1.5                                                                            1/1  1/1                       second agent)                                                                 Weight ratio (anionic surface active                                                           5/5  5/5  6/4  5/5  6/4  5/5  5/5  6/4                       agent/amphoteric surface active agent)                                        pH at the time of mixing                                                                         9.5                                                                                9.3                                                                                9.2                                                                                9.3                                                                                9.5                                                                                9.5                                                                                7.5                                                                                7.8                     Dyeability       ++   ++   ++   ++   ++   ++   ++   ++                        Dryness to the touch                                                                           ++   ++   ++   ++   ++   ++   ++   ++                        Viscosity of the first agent                                                                   100  120  110  80   130  110  120  150                       Viscosity of the second agent                                                                  40   40   40   30   40   30   40   40                        Viscosity after mixing                                                                         3000 5500 7000 4500 3500 2500 8500 6400                      Low temperature stability                                                                      ++   ++   ++   ++   ++   ++   ++   ++                        __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________                     Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    18   19   20   21   22   23   24   25                        __________________________________________________________________________    (The first agent)                                                             Undecyl-N-hydroxy-N-carboxy-                                                                   2    2    2    2    1    5    5    2                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            6    --   8    2    4    2    11   8                         Sodium Lauroamphoacetate                                                                       --   --   --   --   --   3    --   --                        Oleic acid       3    3    3    3    3    3    3    2                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   --                        product)                                                                      Monoethanolamine 1    2    2    2    2    2    2    1                         Ammonia water (28%)                                                                            15   10   5    10   10   10   11   6                         L-ascorbic acid    0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                     Paraphenylenediamine                                                                           1    1    1    1      0.5                                                                              1      0.5                                                                              1                         Resorcinol         0.5                                                                              1    1      0.5                                                                              1    1    1    1                         1,3-Butylene glycol                                                                            1      0.5                                                                              3    1      0.5                                                                              2      0.5                                                                                2.5                     Ethanol          --   --   --   --   --   --   --     0.5                     Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            Triethanolammonium polyoxyethylene                                                             2    --   8    4    1    6    --   5                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       8    18   2    12   4    --   10   5                         Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   4    --   --                        O- 2-hydroxy-3-(trimethylammonio)-                                                             --   --   --   --   --   --   --   --                        propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                  --   --   --   --   --   --   --   --                        polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --   --   --   --   --   --                        acrylamide copolymer                                                          Vinyl pyrrolidone-N,N-                                                                         --   --   --   --   --   --   --   --                        dimethylaminoethyl methacrylate-                                              stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp--                                                                           Approp--                                                                           Approp--                                   riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1  1/1    1/1.5                                                                            1/1                       second agent)                                                                 Weight ratio (anionic surface active                                                           5/5  9/1  6/4  8/2  5/5  5/5  5/5  5/5                       agent/amphoteric surface active agent)                                        pH at the time of mixing                                                                       11.5   9.3                                                                                8.3                                                                                9.4                                                                                9.2                                                                                9.3                                                                                9.4                                                                              9                         Dyeability       ++   ++   ++   ++   ++   ++   ++   ++                        Dryness to the touch                                                                           +    ++   ++   ++   ++   ++   ++   ++                        Viscosity of the first agent                                                                   90   60   120  80   70   100  180  120                       Viscosity of the second agent                                                                  30   40   45   35   20   30   40   40                        Viscosity after mixing                                                                         1200 3500 7000 2800 600  800  4500 5400                      Low temperature stability                                                                      ++   ++   ++   ++   ++   ++   ++   ++                        __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________                     Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                   tive tive tive tive tive tive tive tive                                       Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    2    3    4    5    6    7    8    9                         __________________________________________________________________________    (The first agent)                                                             Undecyl-N-hydroxy-N-carboxy-                                                                   14   --   7    --   5    10   2    8                         methylidazolinium betaine                                                     Cocoyl Amide Propyldimethyl Glycine                                                            --   14   --   --   5    --   6    6                         Sodium Lauroamphoacetate                                                                       --   --   --   --   --   --   --   --                        Oleic acid       2    3    3    --   3    3    --   2                         Sodium polyoxyethylene (1,5) alkyl                                                             --   --   --   --   --   --   --   --                        (12,14) ether sulfate                                                         Polyoxyethylene (2) oleyl ether                                                                --   --   5    5    --   5    --   --                        Polyoxyethylene (5) octylphenyl ether                                                          --   --   --   --   --   5    --   --                        Sodium alkylbenzenesulfonate                                                                   --   --   --   --   --   --   --   5                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   1                         product)                                                                      Monoethanolamine 1    2    2    2    2    2    2    3                         Ammonia water (28%)                                                                            10   10   10   10   12   10   10   10                        L-ascorbic acid    0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                     Paraphenylenediamine                                                                           1    1      0.5                                                                              1    1    1    1    1                         Resorcinol       --   1    1    1    1    1      0.5                                                                              1                         1,3-Butylene glycol                                                                            --   --   --   --   --   --   --   --                        Ethanol          --   --   --   --   --   --   --   10                        Isopropanol      8    --   --   --   --   --   --   --                        Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            Triethanolammonium polyoxyethylene                                                             6    6    3    10   --   --   8    5                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       --   --   --   --   --   --   --   3                         Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   --   --   --                        O- 2-hydroxy-3-(trimethylammonio)-                                                             --   --   --   --   --   --   --   --                        propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                  --   --   --   --   --   --   --   --                        polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --   --   --   --   --   --                        acrylamide copolymer                                                          Vinylpyrrolidone-N,N-                                                                          --   --   --   --   --   --   --   --                        dimethylaminoethyl methacrylate-                                              stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1  1/1  1/1  1/1                       second agent)                                                                 Weight ratio (anionic surface                                                                  3/7  3/7  3/7  10/0  0/10                                                                               0/10                                                                              5/5  4/6                       active agent/amphoteric surface                                               active agent)                                                                 pH at the time of mixing                                                                         9.4                                                                                9.5                                                                                9.2                                                                                9.8                                                                                9.8                                                                                9.3                                                                                9.8                                                                                9.8                     Dyeability       ++   ++   +    +    ± ± ++   +                         Dryness to the touch                                                                           ++   -    ± ± ++   -    +    -                         Viscosity of the first agent                                                                   100  130  110  80   120  100  140  50                        Viscosity of the second agent                                                                  40   40   30   30   20   30   20   20                        Viscosity after mixing                                                                         200  300  1000 1500 200  1400 1200 400                       Low temperature stability                                                                      ++   ++   ± ± -    ± -    +                         __________________________________________________________________________

As apparent from the above Tables 1 to 4, the hair dyes of the inventionare excellent in dyeability, and free from dryness to the touch, and forexample, when they are prepared as the first agent and the second agent,they are low in viscosity, respectively, moderate in the viscosity aftermixing and moreover excellent in low temperature stability. Further, inall of the hair dyes of the invention, good thickening effect wasascertained, all of them exhibited viscosities of 500 cps or more, andit is seen that they have high thickening effect.

Example 26 and Comparative Example 10 (Usual System)

In the following example, the effects of the composition of theinvention in the case where an anionic surface active agent is used inmixing with the first agent are illustrated.

The following first agent and the second agent of the invention or ausual system were mixed in a ratio of 1:1 to prepare a hair dye, andusing hair strands, the difference in dyeability between the inventionand the usual system was evaluated based on relations between time forwhich the hair strands were left alone and the L value. Further, theviscosities of the first agent and the second agent, and the viscosityafter mixing of both were measured.

    ______________________________________                                                           (weight %)                                                 ______________________________________                                         The first agent! (Example 26)                                                Sodium polyoxyethylene (1.5) alkyl                                                                 16.0                                                     (12, 14) ether sulfate                                                        Undecyl-N-hydroxyethyl-N-                                                                          4.0                                                      carboxymethylimidazolinium betaine                                            Oleic acid           5.0                                                      Monoethanolamine     3.0                                                      L-ascorbic acid      0.5                                                      Paraphenylenediamine 1.0                                                      Resorcinol           1.0                                                      Perfume              Appropriate amount                                       Purified water       Balance                                                  Total                100.0                                                     The first agent! (Comparative example 10)                                    Polyoxyethylene (2) oleyl ether                                                                    15.0                                                     Polyoxyethylene (5) octylphenyl ether                                                              5.0                                                      Oleic acid           10.0                                                     Monoethanolamine     3.0                                                      Paraphenylenediamine 1.0                                                      Resorcinol           1.0                                                      L-ascorbic acid      1.5                                                      Sodium sulfite       0.1                                                      Perfume              Appropriate amount                                       Purified water       Balance                                                  Total                100.0                                                     The second agent!                                                            Aqueous hydrogen peroxide (30%)                                                                    20.0                                                     Methylparaben        Appropriate amount                                       Sodium stannate      Appropriate amount                                       Phosphate buffer     Adjusted to pH 2                                         Purified water       Balance                                                  Total                100.0                                                    ______________________________________                                    

The L value at 20 minutes after the treatment with Example 26 was 13.2and that in the case of the comparative example was 16.5, and also byvisual observation, the product of the invention was found to besuperior to the usual system in dyeability.

Next, the dyed hair was irradiated with carbon arc for 20 hours or witha xenon lamp for 30 hours, and change of L values (ΔL) was checked. InComparative example 10, ΔL was 12.0 (xenon), whereas in Example 26, ΔLwas 6.0 (xenon), and the hair dyed with the present example was found tobe slow to discolor.

Further, as to the first agent of Example 26, the pH was 9.83 and theviscosity was 300 cps, and as to the second agent, the pH was 2.1 andthe viscosity was 10 cps, and after both were mixed, the pH became 7.8and the viscosity became 7,200 cps, and remarkable thickening effect wasobserved.

Next, the first agent and the second agent of Example 26 were used, andan appropriate amount of a pH-adjusting agent (ammonia water orphosphoric acid) was added at the time of mixing to prepare hair dyes ofpH 5, 6 and 12, respectively. When viscosity was measured, theviscosities of these hair dyes were 400 cps, 3,000 cps and 1,070 cps,respectively, and it was found that in the hair dyes of the inventionwherein the pH is 6 to 12, excellent thickening effect can be obtained.Further, the L values at 20 minutes after the hair dyeing treatment were45, 20 and 20, respectively, and it was revealed that dyeability is highin the range of pH 6 to 12.

Examples 27 to 39 and Comparative Examples 11 to 24

Evaluation was made according to the above-mentioned evaluation methodon hair dyes obtained by mixing the first agents having variouscompositions with the second agent used in Example 26. The results areshown together in Tables 5 to 9.

                                      TABLE 5                                     __________________________________________________________________________                              Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                         (The first agent)         27   28   29   30   31                              __________________________________________________________________________    Triethanolammonium polyoxyethylene                                                                      8    10   12   18   16                              (2) alkyl (12,14) ether sulfate                                               Polyoxyethylene (2) oleyl ether                                                                         --   --   --   --   --                              Polyoxyethylene (5) octylphenyl ether                                                                   --   --   --   --   --                              Undecyl-N-hydroxy-N-      2    --   4    --   4                               carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                     --   --   4    2    --                              Sodium Lauroamphoacetate  --   --   --   --   --                              Oleic acid                2    3    3    4    3                               Isostearic acid (Emery #871 desalted product)                                                           --   --   --   --   --                              Isopropanol               --   --   --   --   --                              Monoethanolamine          2    2    2    2    1                               Ammonia water (28%)       --   10   9    1    20                              L-ascorbic acid             0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                           Paraphenylenediamine        1.0                                                                                1.0                                                                                1.0                                                                                1.0                                                                                1.0                           Resorcinol                --     1.0                                                                                1.0                                                                                1.0                                                                                1.0                           Purified water            to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                          Weight ratio (anionic surface active agent/amphoteric                                                   8/2  10/0 6/4  9/1  8/2                             surface active agent)                                                         pH at the time of mixing    7.2                                                                                9.1                                                                                8.2                                                                                7.3                                                                                10.5                          Dyeability                ++   ++   ++   ++   ++                              Dryness to the touch      ++   ++   ++   ++   ++                              Viscosity after mixing    7000 5500 7000 5500 6000                            Low temperature stability ++   ++   ++   ++   ++                              __________________________________________________________________________

                                      TABLE 6                                     __________________________________________________________________________                              Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                         (The first agent)         32   33   34   35   36                              __________________________________________________________________________    Triethanolammonium polyoxyethylene (2) alkyl                                                            14   15   16   8    14                              (12,14) ether sulfate                                                         Sodium lauryl ether sulfate                                                                             --   --   --   --   --                              Polyoxyethylene (2) oleyl ether                                                                         --   --   --   --   --                              Polyoxyethylene (5) octylphenyl ether                                                                   --   --   --   --   --                              Undecyl-N-hydroxy-N-carboxymethylimidazolinium betaine                                                  2    --   1    2    --                              Cocoyl Amide Propyldimethyl Glycine                                                                     --   --   1    --   2                               Sodium Lauroamphoacetate  4    --   1    --   2                               Oleic acid                2    2    1    3    2                               Isostearic acid (Emery #871 desalted product)                                                           --   1    1    --   1                               Isopropanol               --   --   --   --   --                              Monoethanolamine          1    1    2    2    1                               Ammonia water (28%)       5    1    10   10   10                              L-ascorbic acid             0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                           Paraphenylenediamine        1.0                                                                                1.0                                                                                1.0                                                                                1.0                                                                                1.0                           Resorcinol                --     1.0                                                                                1.0                                                                                1.0                                                                                1.0                           Purified water            to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                          Weight ratio (anionic surface active agent/amphoteric                                                   7/3  10/0 8/2  8/2  7/3                             surface active agent)                                                         pH at the time of mixing    8.5                                                                                7.2                                                                                9.9                                                                                9.4                                                                                8.6                           Dyeability                ++   ++   ++   ++   ++                              Dryness to the touch      ++   ++   ++   ++   ++                              Viscosity after mixing    4000 5500 7000 800  7500                            Low temperature stability ++   ++   ++   ++   ++                              __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________    (The first agent)         Example 37                                                                          Example 38                                                                          Example 39                              __________________________________________________________________________    Triethanolammonium polyoxyethylene (2) alkyl                                                            16    16    --                                      (12,14) ether sulfate                                                         Sodium lauryl ether sulfate                                                                             --    --    12                                      Polyoxyethylene (2) oleyl ether                                                                         --    --    --                                      Polyoxyethylene (5) octylphenyl ether                                                                   --    --    --                                      Undecyl-N-hydroxy-N-carboxymethylimidazolinium betaine                                                  2     2     4                                       Cocoyl Amide Propyldimethyl Glycine                                                                     2     2     4                                       Sodium Lauroamphoacetate  --    --    --                                      Oleic acid                3     3     3                                       Isostearic acid (Emery #871 desalted product)                                                           --    --    --                                      Isopropanol                 1.5   3.0 --                                      Monoethanolamine          2     2     2                                       Ammonia water (28%)       10    10    9                                       L-ascorbic acid             0.5   0.5   0.5                                   Paraphenylenediamine        1.0   1.0   1.0                                   Resorcinol                  0.2   0.2   0.2                                   Purified water            to 100                                                                              to 100                                                                              to 100                                  Weight ratio (anionic surface active agent/amphoteric                                                   8/2   8/2   6/4                                     surface active agent)                                                         pH at the time of mixing    9.0   8.9   8.5                                   Dyeability                ++    ++    ++                                      Dryness to the touch      +     +     +                                       Viscosity after mixing    2300  2300  2500                                    Low temperature stability ++    ++    ++                                      __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________                              Comparative                                                                         Comparative                                                                         Comparative                                                                         Comparative                                                                         Comparative                                                                         Comparative           (The first agent)         Example 11                                                                          Example 12                                                                          Example 13                                                                          Example 14                                                                          Example                                                                             Example               __________________________________________________________________________                                                            16                    Triethanolammonium polyoxyethylene (2) alkyl                                                            10    10    10    --    10    16                    (12,14) ether sulfate                                                         Triethanolammonium polyoxyethylene (2) alkyl                                                            --    --    --    10    --    --                    (12,13) ether sulfate                                                         Polyoxyethylene (2) oleyl ether                                               Polyoxyethylene (5) octylphenyl ether                                                                   --    --    --    --    --    --                    Undecyl-N-hydroxy-N-carboxymethyl imidazolinium betaine                                                 10    --    2     --    10    2                     Cocoyl Amide Propyldimethyl Glycine                                                                     --    10    8     --    --    --                    Sodium Lauroamphoacetate                                                      Oleic acid                2     3     3     --     3    3                     Isostearic acid (Emery #871 desalted product)                                                           --    --    --    --    --    --                    Isopropanol               --    --    5     --    --    4                     Monoethanolamine          1     1     2     2      1    2                     Ammonia water (28%)       12    14    10    10    25    10                    L-ascorbic acid           0.5   0.5     0.5 0.5     0.5   0.5                 Paraphenylenediamine      1.0   1.0     1.0 1.0     1.0   1.0                 Resorcinol                --    1.0     1.0 1.0     1.0   0.2                 Purified water            to 100                                                                              to 100                                                                              to 100                                                                              to 100                                                                              to 100                                                                              to 100                Weight ratio (anionic surface active agent/amphoteric                                                   5/5   5/5   5/5   10/0  10/0  8/2                   surface active agent)                                                         pH at the time of mixing  9.4   9.5   9.2   9.8     12.5                                                                                9.0                 Dyeability                ++    ++    ++    ++    ±  ++                    Dryness to the touch      ++    ++    ±  ±  -     ±                  Viscosity after mixing    400   350   300   120   280   300                   Low temperature stability ++    ++    ±  +     +     ++                    __________________________________________________________________________

                                      TABLE 9                                     __________________________________________________________________________                              Comparative                                                                         Comparative                                                                         Comparative                                                                         Comparative                       (The first agent)         Example 17                                                                          Example 18                                                                          Example 19                                                                          Example 20                        __________________________________________________________________________    Triethanolammonium polyoxyethylene (2) alkyl                                                            --    --    10    --                                (12,14) ether sulfate                                                         Triethanolammonium behenyl ether sulfate                                                                5     --    --    --                                Polyoxyethylene (2) oleyl ether                                                                         5     --    5     5                                 Polyoxyethylene (5) octylphenyl ether                                                                   --    --    --    5                                 Undecyl-N-hydroxy-N-carboxymethylimidazolinium betaine                                                  --    5     2     --                                Cocoyl Amide Propyldimethyl Glycine                                                                     --    5     8     --                                Sodium Lauroamphoacetate                                                      Oleic acid                5     3     3     4                                 Isostearic acid (Emery #871 desalted product)                                                           --    --    --    --                                Isopropanol               --    --    5     8                                 Monoethanolamine          1     1     2     2                                 Ammonia water (28%)       10    10    10    1                                 L-ascorbic acid           0.5   0.5   0.5   0.5                               Paraphenyl enediamine     1.0   1.0   1.0   1.0                               Resorcinol                --    1.0   1.0   1.0                               Purified water            to 100                                                                              to 100                                                                              to 100                                                                              to 100                            Weight ratio (anionic surface active agent/amphoteric                                                   10/0  0/10  5/5   6/4                               surface active agent)                                                         pH at the time of mixing  9.0   9.1   8.9   7.9                               Dyeability                +     --    ±  -                                 Dryness to the touch      +     ++    -     -                                 Viscosity after mixing    300   300   1000  1200                              Low temperature stability -     +     ±  -                                 __________________________________________________________________________                              Comparative                                                                         Comparative                                                                         Comparative                                                                         Comparative                       (The first agent)         Example 21                                                                          Example 22                                                                          Example 23                                                                          Example 24                        __________________________________________________________________________    Triethanolammonium polyoxyethylene (2) alkyl                                                            --    --    10    12                                (12,14) ether sulfate                                                         Triethanolammonium behenyl ether sulfate                                                                --    10    --    --                                Polyoxyethylene (2) oleyl ether.                                                                        5     --    --    --                                Polyoxyethylene (5) octylphenyl ether                                                                   5     --    --    --                                Undecyl-N-hydroxy-N-carboxymethyl imidazolinium betaine                                                 10    --    --    4                                 Cocoyl Amide Propyldimethyl Glycine                                                                     --    --    --    4                                 Sodium Lauroamphoacetate  --    --    --    --                                Oleic acid                3     3     --    --                                Isostearic acid (Emery #871 desalted product)                                                           --    --    --    --                                Isopropanol               --    --    --    --                                Monoethanolamine          1     2     2     2                                 Ammonia water (28%)       5     10    8     9                                 L-ascorbic acid           0.5   0.5   0.5   0.5                               Paraphenylenediamine      1.0   1.0   1.0   1.0                               Resorcinol                1.0   --    1.0   1.0                               Purified water            to 100                                                                              to 100                                                                              to 100                                                                              to 100                            Weight ratio (anionic surface active agent/amphoteric                                                   0/10  10/0  10/0  6/4                               surface active agent)                                                         pH at the time of mixing  8.3   9.3   9.2   8.8                               Dyeability                ±  ±  +     +                                 Dryness to the touch      ±  ++    +     +                                 Viscosity after mixing    1700  180   120   1100                              Low temperature stability ±  +     +     -                                 __________________________________________________________________________

As apparent from the above Tables 5 to 9, the hair dyes of the inventionare excellent in dyeability, and free from dryness to the touch, and forexample, when they are prepared as the first agent and the second agent,they are low in viscosity, respectively, moderate in the viscosity aftermixing and moreover excellent in low temperature stability. Further, inall of the hair dyes of the invention, good thickening effect wasascertained, all of them exhibited viscosities of 500 cps or more, andit is seen that they have high thickening effect.

Example 40 and Comparative Example 25 (Usual System)

In the following example, the effects of the composition of theinvention wherein two or more of amphoteric surface active agents orsemipolar surface active agents are used in combination are illustrated.

The following first agent and the second agent of the invention or ausual system were mixed in a ratio of 1:1 to prepare a hair dye, andusing hair strands, the difference in dyeability between the inventionand the usual system was evaluated based on relations between time forwhich the hair strands were left alone and the L value.

Further, the viscosities of the first agent and the second agent, andthe viscosity after mixing of both were measured.

    ______________________________________                                                           (weight %)                                                 ______________________________________                                         The first agent! (Example 40)                                                Sodium polyoxyethylene (1.5) alkyl                                                                 10.0                                                     (12, 14) ether sulfate                                                        Undecyl-N-hydroxyethyl-N-                                                                          3.0                                                      carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                7.0                                                      Oleic acid           3.0                                                      Monoethanolamine     2.0                                                      Ammonia water (28%)  10.0                                                     L-ascorbic acid      0.5                                                      Paraphenylenediamine 1.0                                                      Resorcinol           1.0                                                      Perfume              Appropriate amount                                       Purified water       Balance                                                  Total                100.0                                                     The first agent! (Comparative example 25)                                    Polyoxyethylene (2) oleyl ether                                                                    15.0                                                     Polyoxyethylene (5) octylphenyl ether                                                              5.0                                                      Oleic acid           10.0                                                     Monoethanolamine     2.0                                                      Ammonia water (28%)  10.0                                                     Paraphenylenediamine 1.0                                                      Resorcinol           1.0                                                      L-ascorbic acid      0.5                                                      Sodium hydrosulfite  0.1                                                      Perfume              Appropriate amount                                       Purified water       Balance                                                  Total                100.0                                                     The second agent!                                                            Aqueous hydrogen peroxide (30%)                                                                    20.0                                                     Methyl paraben       Appropriate amount                                       EDTA                 Appropriate amount                                       Phosphate buffer     Adjusted to pH 3                                         Purified water       Balance                                                  Total                100.0                                                    ______________________________________                                    

The L value at 20 minutes after the treatment with the hair dye ofExample 40 was 14.3 and that in the case of the comparative example was17.8, and also by visual observation, the product of the invention wasfound to be superior to the usual system in dyeability.

Next, the dyed hair was irradiated with carbon arc for 20 hours or witha xenon lamp for 30 hours, and change of L values (ΔL) was checked. InComparative example 25, ΔL was 12.0 (xenon), whereas in Example 40, ΔLwas 4.2 (xenon), and the hair dyed with the present example was found tobe slow to discolor.

Further, as to the first agent of Example 40 , the pH was 10.85 and theviscosity was 260 cps, and as to the second agent, the pH was 2.1 andthe viscosity was 8 cps, and after both were mixed, the pH became 9.3and the viscosity became 6,500 cps, and remarkable thickening effect wasobserved.

Next, the first agent and the second agent of Example 40 were used, andan appropriate amount of a pH-adjusting agent (ammonia water orphosphoric acid) was added at the time of mixing to prepare hair dyes ofpH 5, 6 and 12, respectively. When viscosity was measured, theviscosities of these hair dyes were 480 cps, 1,220 cps and 1,030 cps,respectively, and it was found that in the hair dyes of the inventionwherein the pH is 6 to 12, excellent thickening effect can be obtained.Further, the L values at 20 minutes after the hair dyeing treatment were50, 25 and 36, respectively, and it was revealed that dyeability is highin the range of pH 6 to 12.

Examples 41 to 56 and Comparative Examples 26 to 35

Evaluation was made according to the abovementioned evaluation method onhair dyes obtained by mixing the first agents having variouscompositions with the second agent used in Example 40. The results areshown together in Tables 10 to 14.

Comparative examples herein referred to are examples of the inventionexcept for Comparative example 32, but they were classified ascomparative examples in view of comparison with specific combination useof amphoteric surface active agents or semipolar surface active agents.

                                      TABLE 10                                    __________________________________________________________________________                              Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                    (The first agent)         41   42   43   44   45   46                         __________________________________________________________________________    Triethanolammonium polyoxyethylene (2) alkyl                                                            8    10   15   10   10   10                         (12,14) ether sulfate                                                         Polyoxyethylene (2) oleyl ether                                               Polyoxyethylene (5) octylphenyl ether                                                                   --   --   --   --   --   --                         Undecyl-N-hydroxy-N-carboxymethylimidazolinium betaine                                                  2    1    2    3    4    4                          Cocoyl Amide Propyldimethyl Glycine                                                                     6    9    8    12   6    6                          Sodium Lauroamphoacetate  --   --   --   --   --   --                         Oleic acid                2    3    3    4    3    3                          Isostearic acid (Emery #871 desalted product)                                                           --   --   --   --   --   --                         Isopropanol               --   --   --   --   --   --                         Monoethanolamine          1    2    2    2    1    1                          Ammonia water (28%)       10   10   10   10   10   15                         L-ascorbic acid           0.5  0.5  0.5  0.5  0.5  0.5                        Paraphenyl enediamine     1.0  1.0  1.0  1.0  1.0  1.0                        Resorcinol                --   1.0  1.0  1.0  1.0  1.0                        Purified water            to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                     Weight ratio (anionic surface active agent/amphoteric                                                   5/5  5/5  6/4  4/6  5/5  5/5                        surface active agent)                                                         pH at the time of mixing  9.5  9.3  9.2  8.9  9.3  9.6                        Dyeability                ++   ++   ++   ++   ++   ++                         Dryness to the touch      ++   ++   ++   ++   ++   ++                         Viscosity after mixing    3000 5500 7000 5500 6000 700                        Low temperature stability ++   ++   ++   ++   ++   ++                         __________________________________________________________________________

                                      TABLE 11                                    __________________________________________________________________________                              Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                         (The first agent)         47   48   49   50   51                              __________________________________________________________________________    Triethanolammonium polyoxyethylene (2) alkyl                                                            10   10   10   10   10                              (12,14) ether sulfate                                                         Polyoxyethylene (2) oleyl ether                                                                         --   --   --   --   --                              Polyoxyethylene (5) octylphenyl ether                                                                   --   --   --   --   --                              Undecyl-N-hydroxy-N-carboxymethylimidazolinium betaine                                                  2    2    3    5    8                               Cocoyl Amide Propyldimethyl Glycine                                                                     --   2    4    --   1                               Sodium Lauroamphoacetate  8    6    3    5    1                               Oleic acid                2    2    3    3    2                               Isostearic acid (Emery #871 desalted product)                                                           --   1    1    --   1                               Isopropanol               --   --   --   --   --                              Monoethanolamine          1    1    2    2    1                               Ammonia water (28%)       10   10   10   10   10                              L-ascorbic acid           0.5  0.5  0.5  0.5  0.5                             Paraphenyl enediamine     1.0  1.0  1.0  1.0  1.0                             Resorcinol                --   1.0  1.0  1.0  1.0                             Purified water            to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                          Weight ratio (anionic surface active agent/amphoteric                                                   5/5  5/5  5/5  5/5  5/5                             surface active agent)                                                         pH at the time of mixing  9.4  9.2  8.9  9.3  9.2                             Dyeability                ++   ++   ++   ++   ++                              Dryness to the touch      ++   ++   ++   ++   ++                              Viscosity after mixing    7000 8500 6500 5500 6000                            Low temperature stability ++   ++   ++   ++   ++                              __________________________________________________________________________

                                      TABLE 12                                    __________________________________________________________________________                              Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                         (The first agent)         52   53   54   55   56                              __________________________________________________________________________    Triethanolammonium polyoxyethylene (2) alkyl                                                            12   12   10   10   10                              (12,14) ether sulfate                                                         Undecyl-N-hydroxy-N-carboxymethylimidazolinium betaine                                                  8    8    7    7    7                               Cocoyl Amide Propyldimethyl Glycine                                                                     4    4    2    2    2                               Coconut oil fatty acid amidopropyl-N,N-dimethyl-                                                        --   --   1    --   --                              N-sulfopropyl betaine                                                         Lauroyl-N,N-dimethyl-N-sulfopropyl betaine                                                              --   --   --   1    --                              Lauryldimethylamine oxide --   --   --   --   1                               Oleic acid                3    3    2    2    2                               Isostearic acid (Emery #871 desalted product)                                                           --   --   1    1    1                               Isopropanol               1.5  3.0  --   --   --                              Monoethanolamine          2    2    1    1    1                               Ammonia water (28%)       10   10   10   10   10                              L-ascorbic acid           0.5  0.5  0.5  0.5  0.5                             Paraphenyl enediamine     1.0  1.0  --   --   --                              Resorcinol                0.2  0.2  1.0  1.0  1.0                             Purified water            to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                          Weight ratio (anionic surface active agent/amphoteric                                                   5/5  5/5  5/5  5/5  5/5                             surface active agent)                                                         pH at the time of mixing  9.0  9.1  9.1  9.2  9.2                             Dyeability                ++   ++   ++   ++   ++                              Dryness to the touch      +    +    ++   ++   ++                              Viscosity after mixing    3000 3000 4500 4700 3800                            Low temperature stability ++   ++   ++   ++   ++                              __________________________________________________________________________

                                      TABLE 13                                    __________________________________________________________________________                               Comparative                                                                         Comparative                                                                         Comparative                                                                         Comparative                                                                         Comparative                                                                         Comparative          (The first agent)          Example 26                                                                          Example 27                                                                          Example 28                                                                          Example 29                                                                          Example                                                                             Example              __________________________________________________________________________                                                             31                   Triethanolammonium polyoxyethylene (2) alkyi                                                             6     6     6     0     3     12                   (12, 14) ether sulfate                                                        Polyoxyethylene (2) oleyl ether                                                                          --    --    --    --    --    --                   Polyoxyethylene (5) octylphenyl ether                                                                    --    --    --    --    5     --                   Undecyl-N-hydroxy-N-carboxymethylimidazolinium betaine                                                   14    --    6     10    7     8                    Cocoyl Amide Propyldimethyl Glycine                                                                      --    14    8     --    --    4                    Sodium Lauroamphoacetate   --    --    --    --    --    --                   Oleic acid                 2     3     3     4     3     3                    Isostearic acid (Emery #871 desalted product)                                                            --    --    --    --    --    --                   Isopropanol                --    --    5     4     --    4                    Monoethanolamine           1     1     2     2     1     2                    Ammonia water (28%)        10    10    10    10    10    10                   L-ascorbic acid            0.5   0.5   0.5   0.5   0.5                        Paraphenyl enediamine      1.0   1.0   1.0   1.0   1.0   1.0                  Resorcinol                 --    1.0   1.0   1.0   1.0   0.2                  Purified water             to 100                                                                              to 100                                                                              to 100                                                                              to 100                                                                              to 100                     Weight ratio (anionic surface active agent/amphoteric                                                    3/7   3/7   3/7   0/10  3/7   5/5                  surface active agent)                                                         pH at the time of mixing   9.4   9.5   9.0   8.9   9.2   9.1                  Dyeability                 ++    ++    ++    ++    +     ++                   Dryness to the touch       ++    ++    ±  ±  ±  ±                 Viscosity after mixing     200   300   250   1000  1200  400                  Low temperature stability  ++    ++    ±  -     ±  ++                   __________________________________________________________________________

                                      TABLE 14                                    __________________________________________________________________________                              Comparative                                                                         Comparative                                                                         Comparative                                                                         Comparative                       (The first agent)         Example 32                                                                          Example 33                                                                          Example 34                                                                          Example 35                        __________________________________________________________________________    Triethanolammonium polyoxyethylene (2) alkyl                                                            10    --    --    8                                 (12,14) ether sulfate                                                         Polyoxyethylene (2) oleyl ether                                                                         5     --    5     --                                Polyoxyethylene (5) octylphenyl ether                                                                   --    --    5     --                                Undecyl-N-hydroxy-N-carboxymethylimidazolinium betaine                                                  --    5     10    2                                 Cocoyl Amide Propyldimethyl Glycine                                                                     --    5     --    6                                 Sodium Lauroamphoacetate  --    --    --    --                                Oleic acid                --    3     3     --                                Isostearic acid (Emery #871 desalted product)                                                           --    --    --    --                                Isopropanol               --    --    --    --                                Monoethanolamine          1     1     1     1                                 Ammonia water (28%)       10    10    10    10                                L-ascorbic acid           0.5   0.5   0.5   0.5                               Paraphenyl enediamine     1.0   1.0   1.0   1.0                               Resorcinol                --    1.0   1.0   --                                Purified water            to 100                                                                              to 100                                                                              to 100                                                                              to 100                            Weight ratio (anionic surface active agent/amphoteric                                                   --    --    --    5/5                               surface active agent)                                                         pH at the time of mixing  9.8   9.8   9.3   9.8                               Dyeability                +     ±  ±  ++                                Dryness to the touch      --    ++    ±  +                                 Viscosity after mixing    110   200   1400  1200                              Low temperature stability ±  +     ±  ±                              __________________________________________________________________________

As apparent from the above Tables 10 to 14, the hair dyes of theinvention are excellent in dyeability, and free from dryness to thetouch, moderate in the viscosity after mixing and moreover excellent inlow temperature stability. Further, in all of the hair dyes of theinvention, good thickening effect was ascertained, and particularly, asto hair dyes containing an imidazolinium betaine-type surface activeagent together with an amidobetaine-type, amidosulfobetaine-type,betaine-type or sulfobetaine-type surface active agent or a tertiaryamine oxide-type semipolar surface active agent as the amphotericsurface active agent and/or the semipolar surface active agent, all ofthem exhibited viscosities of 500 cps or more, and it is seen that theyhave high thickening effect.

Example 57 and Comparative Examples 36 and 37 (Usual System)

The effects of the composition of the invention wherein a cationicpolymer is used as an additional component is illustrated.

The following first agent and the second agent of the invention or ausual system were mixed in a ratio of 1:1 to prepare a hair dye, andusing hair strands, the difference in dyeability between the inventionand the usual system was evaluated based on relations between time forwhich the hair strands were left alone and the L value.

Further, the viscosities of the first agent and the second agent, andthe viscosity after mixing of both were measured.

    ______________________________________                                                           (weight %)                                                 ______________________________________                                         The first agent! (Prescription 1-A)                                          Sodium polyoxyethylene (1.5) alkyl                                                                   10.0                                                   (12, 14) ether sulfate                                                        Undecyl-N-hydroxyethyl-N-                                                                            5.0                                                    carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                  5.0                                                    Oleic acid             3.0                                                    Propylene glycol       5.0                                                    Monoethanolamine       2.0                                                    Ammonia water (28%)    10.0                                                    The first agent! (Prescription 1-B)                                          Polyoxyethylene (3) oleyl ether                                                                      15.0                                                   Polyoxyethylene (4) octylphenyl ether                                                                5.0                                                    Ethanol                10.0                                                   Monoethanolamine       2.0                                                    Ammonia water (28%)    5.0                                                    Paraphenylenediamine   2.0                                                    Purified water         Balance                                                Total                  100.0                                                   The second agent! (Prescription 2-A)                                         Aqueous hydrogen peroxide (30%)                                                                      20.0                                                   Methyl paraben         0.1                                                    Sodium stannate        0.1                                                    O- 2-hydroxy-3-(trimethyl ammoniapropyl!                                                             1.0                                                    hydroxycellulose chloride  Polymer JR-400                                     (produced by Union Carbide Co.)!                                              Phosphate buffer       Adjusted to pH 2                                       Purified water         Balance                                                Total                  100.0                                                   The second agent! (Prescription 2-B)                                         Aqueous hydrogen peroxide (30%)                                                                      20.0                                                   Methylparaben          0.1                                                    Sodium stannate        0.1                                                    Phosphate buffer       Adjusted to pH 2                                       Purified water         Balance                                                Total                  100.0                                                  ______________________________________                                                               Comparative                                                                              Comparative                                             Example 57 example 36 example 37                                  ______________________________________                                        The first agent                                                                           Prescription                                                                             Prescription                                                                             Prescription                                            1-A        1-B        1-A                                         The second agent                                                                          Prescription                                                                             Prescription                                                                             Prescription                                            2-A        2-B        2-B                                         Viscosity of                                                                                150      70         150                                         the first agent                                                               Viscosity of                                                                                40       40          15                                         the second agent                                                              Viscosity at the                                                                          2,800      2,500      450                                         time of mixing                                                                Dyeability  ++         ±       ++                                          Dryness to the touch                                                                      ++         -          ++                                          Low temperature                                                                           ++         +          ++                                          stability                                                                     ______________________________________                                    

The L value at 20 minutes after the treatment with Example 57 was 12.9and that in the case of Comparative example 36 was 16.1, and also byvisual observation, the product of the invention was found to besuperior to the usual system in dyeability.

Further, as to the first agent of Example 57, the pH was 11.2 and theviscosity was 150 cps, and as to the second agent, the pH was 2.0 andthe viscosity was 40 cps, and after both were mixed, the pH became 9.5and the viscosity became 2,800 cps, and remarkable thickening effect wasobserved.

Next, the first agent and the second agent of Example 57 were used, andan appropriate amount of a pH-adjusting agent (ammonia water orphosphoric acid) was added at the time of mixing to prepare hair dyes ofpH 5, 6 and 12, respectively. When viscosity was measured, theviscosities of these hair dyes were 300 cps, 1,500 cps and 650 cps,respectively, and it was found that in the hair dyes of the inventionwherein the pH is 6 to 12, excellent thickening effect can be obtained.Further, the L values at 20 minutes after the hair dyeing treatment were24.0, 12.0 and 15.2, respectively, and it was revealed that dyeabilityis high in the range of pH 6 to 12.

Examples 58 to 81 and Comparative Examples 38 to 45

Evaluation was made according to the above-mentioned evaluation methodon hair dyes obtained by mixing the first agents having variouscompositions with the second agents having various compositions shown inTable 15 to Table 18. All of the pH values of the hair dyes in Tables 15to 17 were 6 to 12.

                                      TABLE 15                                    __________________________________________________________________________                     Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    58   59   60   61   62   63   64   65                        __________________________________________________________________________    (The first agent)                                                             Triethanolammonium polyoxyethylene                                                             8    10   15   10   10   10   10   8                         (2) alkyl (12, 14) ether sulfate                                              Sodium α-alkenyl (12,13) sulfonate                                                       --   --   --   --   --   --   --   --                        Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   --   --   --                        Undecyl-N-hydroxy-N-carboxy-                                                                   8    --   2    3    4    3    5    4                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            --   --   8    12   --   7    5    8                         Sodium Lauroamphoacetate                                                                       --   --   --   --   6    --                                  Oleic acid       2    3    3    3    3    3    4                              Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   --                        product)                                                                      Monoethanolamine 1    2    2    2    2    2    2    1                         Ammonia water (28%)                                                                            10   15   10   15   10   15   15   10                        L-ascorbic acid  0.5  0.5  0.5  0.5  0.5  0.5  0.5  0.5                       Sodium hydrosulfite                                                                            --   0.1  --   --   0.1  --   0.1  --                        Paraphenylenediamine                                                                           1    1    0.5  1    1    1    1.5  0.8                       Resorcinol       --   1    0.2  0.5  0.5  1    0.8  0.4                       Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            O- 2-hydroxy-3-(trimethylammonio)-                                                             0.1  0.5  --   --   --   0.5  0.2  --                        propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                  --   --   0.5  --   --   --   --   0.2                       polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --   0.5  --   --   --   --                        acrylamide copolymer                                                          Vinylpyrrolidone-N,N-                                                         dimethylaminoethyl methacrylate-                                                               --   --   --   --   0.5  --   0.5  --                        stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methyl paraben   Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1  1/1.5                                                                              1/2  1.5/1                     second agent)                                                                 Weight ratio (anionic surface active                                                           5/5  10/0 6/4  4/6  5/5  5/5  5/5  4/6                       agent/amphoteric surface active agent)                                        pH at the time of mixing                                                                       9.5  9.8  9.2  9.5  9.2  9.2  9    9.4                       Dyeability       ++   ++   ++   ++   ++   ++   ++   ++                        Dryness to the touch                                                                           ++   ++   ++   ++   ++   ++   ++   ++                        Viscosity of the first agent                                                                   100  120  110  150  130  130  150  110                       Viscosity of the second agent                                                                  10   10   10   5    15   16   10   10                        Viscosity after mixing                                                                         3200 1500 4000 2500 1600 1200 800  1500                      Low temperature stability                                                                      ++   ++   ++   ++   ++   ++   ++   ++                        __________________________________________________________________________

                                      TABLE 16                                    __________________________________________________________________________                     Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    66   67   68   69   70   71   72   73                        __________________________________________________________________________    (The first agent)                                                             Triethanolammonium polyoxyethylene                                                             8    10   10   --   --   --   5    5                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       --   --   2    8    8    15   --   3                         Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   --   5    13                        Undecyl-N-hydroxy-N-carboxy-                                                                   2    1    2    2    2    5    4    6                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            6    9    6    4    10   10   6    6                         Sodium Lauroamphoacetate                                                                       --   --   --   2    --   --   --   --                        Oleic acid       2    3    3    3    3    3    3    2                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   1                         product)                                                                      Monoethanolamine 1    2    2    2    2    2    2.5  3                         Ammonia water (28%)                                                                            10   10   10   10   12   10   --   --                        L-ascorbic acid  0.5  0.5  0.5  0.5  0.5  0.5  0.5  0.5                       Paraphenylenediamine                                                                           1    1    0.5  1    1    1    1    1                         Resorcinol       --   1    1    1    1    1    0.5  1                         1,3-Butylene glycol                                                                            2    1    3    2    1.5  2    4.5  4                         Ethanol          --   --   --   --   --   2    --   --                        Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            O- 2-hydroxy-3-(trimethylammonio)-                                            propyl!hydroxyethylcellulose                                                                   --   0.1  0.5  --   0.1  --   --   2                         chloride                                                                      Dimethylmethylenepiperidinium                                                                  0.5  --   --   --   --   0.5  --   --                        polychloride                                                                  Dimethylallyammonium chloride                                                                  --   --   --   --   0.3  0.1  --   --                        acrylamide copolymer                                                          Vinyl pyrrolidone-N,N-                                                        dimethylaminoethyl methacrylate-                                                               --   --   --   --   --   --   0.5  --                        stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methyl paraben   Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1  1/1.5                                                                              1/1  1/1                       second agent)                                                                 Weight ratio (anionic surface active                                                           5/5  5/5  6/4  5/5  6/4  5/5  5/5  6/4                       agent/amphoteric surface active agent)                                        pH at the time of mixing                                                                       9.5  9.3  9.2  9.3  9.5  9.5  7.5  7.8                       Dyeability       ++   ++   ++   ++   ++   ++   ++   ++                        Dryness to the touch                                                                           ++   ++   ++   ++   ++   ++   ++   ++                        Viscosity of the first agent                                                                   100  120  110  80   130  110  120  150                       Viscosity of the second agent                                                                  10   10   10   10   5    10   15   10                        Viscosity after mixing                                                                         2000 4500 4500 1800 2500 1700 800  1200                      Low temperature stability                                                                      ++   ++   ++   ++   ++   ++   ++   ++                        __________________________________________________________________________

                                      TABLE 17                                    __________________________________________________________________________                     Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    74   75   76   77   78   79   80   81                        __________________________________________________________________________    (The first agent)                                                             Triethanolammonium polyoxyethylene                                                             2    --   8    4    1    6    --   5                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       8    18   2    12   4    --   10   5                         Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   4    --   --                        Undecyl-N-hydroxy-N-carboxy-                                                                   2    2    2    2    1    5    5    2                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            6    --   8    2    4    2    5    8                         Sodium Lauroamphoacetate                                                                       --   --   --   --   --   3    --   --                        Oleic acid       3    3    3    3    3    3    3    2                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   --                        product)                                                                      Monoethanolamine 1    2    2    2    2    2    2    1                         Ammonia water (28%)                                                                            15   10   5    10   10   10   11   6                         L-ascorbic acid    0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                     Paraphenylenediamine                                                                           1    1    1    1      0.5                                                                              1      0.5                                                                              1                         Resorcinol         0.5                                                                              1    1      0.5                                                                              1    1    1    1                         1,3-Butylene glycol                                                                            1      0.5                                                                              3    1      0.5                                                                              2      0.5                                                                                2.5                     Ethanol          --   --   --   --   --   --   --     0.5                     Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            O- 2-hydroxy-3-(trimethylammonio)-                                                               0.5                                                                              4    5    2      0.01                                                                               0.2                                                                                0.5                                                                                0.5                     propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                  --   --   --   --   --   --   --   --                        polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --   --   --   --   --     0.1                     acrylamide copolymer                                                          Vinylpyrrolidone-N,N-                                                                          --   --   --   --   --   --     0.5                                                                              --                        dimethylaminoethyl methacrylate-                                              stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1  1/1    1/1.5                                                                            1/1                       second agent)                                                                 Weight ratio (anionic surface active                                                           5/5  9/1  6/4  8/2  5/5  5/5  5/5  5/5                       agent/amphoteric surface active agent)                                        pH at the time of mixing                                                                         11.5                                                                               9.3                                                                                8.3                                                                                9.4                                                                                9.2                                                                                9.3                                                                                9.4                                                                              9                         Dyeability       ++   ++   ++   ++   ++   ++   ++   ++                        Dryness to the touch                                                                           +    ++   ++   ++   ++   ++   ++   ++                        Viscosity of the first agent                                                                   90   60   120  80   70   100  180  120                       Viscosity of the second agent                                                                  30   40   45   35   20   30   110  40                        Viscosity after mixing                                                                         1800 1500 4200 5100 1600 2100 4100 1500                      Low temperature stability                                                                      ++   ++   ++   ++   ++   ++   ++   ++                        __________________________________________________________________________

                                      TABLE 18                                    __________________________________________________________________________                     Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                   tive tive tive tive tive tive tive tive                                       Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    38   39   40   41   42   43   44   45                        __________________________________________________________________________    (The first agent)                                                             Triethanolammonium polyoxyethylene                                                             6    6    3    10   --   --   8    5                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       --   --             --   3                                   Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   --        --                        Undecyl-N-hydroxy-N-                                                                           14        7         5    10   2    6                         carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                            --   14   --        5         6    6                         Sodium Lauroamphoacetate                                                                       --   --   --        --   --   --   --                        Oleic acid       2    3    3         3    3         2                         Polyoxyethylene (2) oleyl ether                                                                --        5    5         5                                   Polyoxyethylene (5) octylphenyl ether                                                          --                       5                                   Sodium alkylbenzenesulfonate                                                                   --                                 5                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   --                        product)                                                                      Monoethanolamine 1    2    2    2    2    2    2    3                         Ammonia water (28%)                                                                            10   10   10   10   12   10   10   10                        L-ascorbic acid    0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5                     Paraphenylenediamine                                                                           1    1      0.5                                                                              1    1    1    1    1                         Resorcinol       1    1    1    1    1      0.5                                                                              1                              1,3-Butylene glycol                                                                            --   --   --                                                 Ethanol          --                            10   10                        Isopropanol      8                             8                              Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            O- 2-hydroxy-3-(trimethylammonio)-                                                               0.5                                                                                0.5                                                                              --     0.2                                                                                0.5                                                                              --     0.2                                                                                0.2                     propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                  --   --     0.5                                                                              --   --     0.5                                                                              --   --                        polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --   --   --   --   --   --                        acrylamide copolymer                                                          Vinyl pyrrolidone-N N-                                                                         --   --   --     0.1                                                                              --   --   --   --                        dimethylaminoethyl methacrylate-                                              stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1  1/1  1/1  1/1                       second agent)                                                                 Weight ratio (anionic surface                                                                  3/7  3/7  3/7  10/0  0/10                                                                               0/10                                                                              5/5  4/6                       active agent/amphoteric surface                                               active agent)                                                                 pH at the time of mixing                                                                         9.4                                                                                9.5                                                                                9.2                                                                                9.8                                                                                9.8                                                                                9.3                                                                                9.8                                                                                9.8                     Dyeability       ++   ++   +    +    ± ± ++   +                         Dryness to the touch                                                                           ++   --   +    +    ++   --   --   --                        Viscosity of the first agent                                                                   100  130  110  80   120  100  140  50                        Viscosity of the second agent                                                                  40   40   30   30   20   30   20   20                        Viscosity after mixing                                                                         200  300  1000 1500 200  1400 200  400                       Low temperature stability                                                                      ++   ++   ± ± +    ± -    +                         __________________________________________________________________________

From the results shown in Table 15 to Table 18, it is seen that the hairdyes of the invention each containing a cationic polymer as anadditional component are also excellent in dyeability, free from drynessto the touch, low in viscosity on the first agent and the second agent,moderate in the viscosity after mixing and moreover excellent in lowtemperature stability. Further, in the usual hair dyes, for making thefirst agent low viscous and obtaining high viscosity at the time ofmixing with the second agent, as shown in Comparative example 36, thenonionic surface active agent is compounded in a high concentration andthe monohydric alcohol (isopropanol) is added so that the viscosity canbe lowered, and heightened at the time of mixing, whereas in theinvention, it is possible to make the first agent low viscous withoutincorporating a monohydric alcohol and attain high viscosity at the timeof mixing.

Example 82 and Comparative Example 46 (Usual System)

In the following example, a further example is mentioned in the casewhere the composition of the invention is adjusted to pH 6 to 8.

The following first agent and the second agent of the invention or ausual system were mixed in a ratio of 3:1 to prepare a hair dye, andusing hair strands, the difference in dyeability between the inventionand the usual system was evaluated based on relations between time forwhich the hair strands were left alone and the L value.

Further, the viscosities of the first agent and the second agent, andthe viscosity after mixing of both were measured.

    ______________________________________                                                              (weight %)                                              ______________________________________                                         The first agent! (Example 82)                                                Sodium Polyoxyethylene (1.5) alkyl                                                                    10.0                                                  (12, 13) ether sulfate                                                        Undecyl-N-hydroxyethyl-N-                                                                             10.0                                                  carboxymethylimidazolinium betaine                                            Oleic acid              3.0                                                   Monoethanolamine        2.0                                                   L-ascorbic acid         0.5                                                   Paraphenylenediamine    2.0                                                   Purified water          Balance                                               Total                   100.0                                                  The first agent! (Comparative example 46)                                    Polyoxyethylene (3) oleyl ether                                                                       15.0                                                  Polyoxyethylene (4) octylphenyl ether                                                                 5.0                                                   Benzyl alcohol          20.0                                                  Monoethanolamine        10.0                                                  L-ascorbic acid         0.5                                                   Paraphenylenediamine    2.0                                                   Purified water          Balance                                               Total                   100.0                                                  The second agent!                                                            Aqueous hydrogen peroxide (30%)                                                                       20.0                                                  Phosphoric acid         0.2                                                   Disodium edetate        0.2                                                   Purified water          Balance                                               Total                   100.0                                                 ______________________________________                                    

The L value at 20 minutes after the treatment with Example 82 was 12.9and that in the case of Comparative example was 16.1, and also by visualobservation, the product of the invention was found to be superior tothe usual system in dyeability.

Further, as to the first agent of Example 82, the pH was 9.5 and theviscosity was 10 cps, and as to the second agent, the pH was 1.5 and theviscosity was 8 cps, and after both were mixed, the pH became 7.2 andthe viscosity became 5,000 cps, and thus it was found that thecomposition of the invention exhibits an enough viscosity not to dropfrom the hair.

Next, the first agent and the second agent of Example 82 were used, andan appropriate amount of a pH-adjusting agent (monoethanolamine orphosphoric acid) was added at the time of mixing to prepare hair dyes ofpH 5, 6 and 8, respectively. When viscosity was measured, theviscosities of these hair dyes were 600 cps, 2,100 cps and 5,900 cps,respectively, and it was found that in the hair dyes of the inventionwherein the pH is 6 to 8, excellent thickening effect can be obtained.Further, the L values at 20 minutes after the hair dyeing treatment were21.0, 12.4 and 11.8, respectively, and it was revealed that dyeabilityis high in the range of pH 6 to 8.

Examples 83 to 88 and Comparative Examples 47 to 50

The first agents of the various compositions shown in Tables 19 and 20and the second agent used in Example 82 (or Comparative example 46) weremixed in a ratio of 3:1 to 1:2 to prepare hair dyes, and using thesehair dyes, evaluation was made according to the above-mentionedevaluation method. All the pH values of the hair dyes in Table 1 were 6to 8. The results are shown together in Tables 19 and 20.

                                      TABLE 19                                    __________________________________________________________________________                              Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                             Example                   (The first agent)         83   84   85   86   87    88                        __________________________________________________________________________    Triethanolammonium polyoxyethylene (2) alkyl (12,14)                                                    8    10   10   12   8     6                         ether sulfate                                                                 Polyoxyethylene (2) oleyl ether                                                                         --   --   --   --   --    --                        Polyoxyethylene (8) octylphenyl ether                                                                   --   --   --   --   --    --                        Undecyl-N-hydroxy-N-carboxymethylimidazolinium betaine                                                  --   10   10   8    12    14                        Sodium Lauroamphoacetate  8    --   --   --   --    --                        Myristic acid             --   2    --   1    --    --                        Isostearic acid (Emery #871 desalted product)                                                           2    --   3    2    3     3                         Isopropanol                                                                   Monoethanolamine            1.0                                                                                1.0                                                                                1.0                                                                                1.0                                                                                1.0   1.0                     L-ascorbic acid             0.5                                                                                0.5                                                                                0.5                                                                                0.5                                                                                0.5   0.5                     Paraphenylenediamine      1    1    1    1    1     1                         Purified water            to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                              to 100                    Weight ratio (anionic surface active agent/amphoteric                                                   5/5  5/5  5/5  6/4  4/6   3/7                       surface active agent)                                                         Dyeability                ++   ++   ++   ++   ++    ++                        Dryness to the touch      ++   ++   ++   ++   ++    +                         Viscosity after mixing    ++   ++   ++   ++   ++    ±                      Low temperature stability ++   +    ++   ++   ++    +                         __________________________________________________________________________

                                      TABLE 20                                    __________________________________________________________________________                              Comparative                                                                         Comparative                                                                         Comparative                                                                         Comparative                       (The first agent)         Example 47                                                                          Example 48                                                                          Example 49                                                                          Example 50                        __________________________________________________________________________    Triethanolammonium polyoxyethylene (2) alkyl (12,14)                                                    --    15    --    --                                ether sulfate                                                                 Polyoxyethylene (2) oleyl ether                                                                         15    --    30    --                                Polyoxyethylene (8) octylphenyl ether                                                                   25    --    --    --                                Undecyl-N-hydroxy-N-carboxymethylimidazolinium betaine                                                  --    --    --    30                                Sodium Lauroamphoacetate  --    --    10    2                                 Myristic acid             --    3     --    --                                Isostearic acid (Emery #871 desalted product)                                                           3     --    2     --                                Isopropanol               10    --    --    --                                Monoethanolamine            1.0   1.0   1.0   1.0                             L-ascorbic acid             0.5   0.5   0.5   0.5                             Paraphenylenediamine      1     1     1     1                                 Purified water            to 100                                                                              to 100                                                                              to 100                                                                              to 100                            Weight ratio (anionic surface active agent/amphoteric                                                   --    --    --    --                                surface active agent)                                                         Dyeability                +     ±  ±  ±                              Dryness to the touch      -     -     -     -                                 Viscosity after mixing    +     -     -     -                                 Low temperature stability -     -     +     ±                              __________________________________________________________________________

From the results shown in Tables 19 to 20, it is seen that the hair dyesof the invention are excellent in dyeability, free from dryness to thetouch, moderate in the viscosity after mixing and moreover excellent inlow temperature stability. Further, in the usual hair dyes, for makingthe first agent low viscous and obtaining high viscosity at the time ofmixing with the second agent, as shown in Comparative example 1, thenonionic surface active agent is compounded in a high concentration andthe monohydric alcohol (isopropanol) is added so that the viscosity canbe lowered, and heightened at the time of mixing, whereas in theinvention, it is possible to make the first agent low viscous withoutincorporating a monohydric alcohol and attain high viscosity at the timeof mixing.

Examples 89 to 107

Further compositions of the invention are shown below. When hair dyeswere prepared using the first agent and the second agent of thecompositions of Example 82, all the viscosities thereof were 500 cps ormore, and it was ascertained that there were excellent effects in all ofdyeability, dryness to the touch, fading properties, low temperaturestability and usability.

Example 89

    ______________________________________                                                            (weight %)                                                ______________________________________                                        (The first agent)                                                             Undecyl-N-hydroxyethyl-N-                                                                           2.0                                                     carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                 8.0                                                     Oleic acid            3.0                                                     Keratin protein hydrolizate                                                                         1.0                                                     Pyrrolidonecarboxylate salt                                                                         1.0                                                     Monoethanolamine      2.0                                                     Ammonia water (28%)   10.0                                                    L-ascorbic acid       0.5                                                     Paraphenylenediamine  1.0                                                     Resorcinol            1.0                                                     Metaaminophenol       0.5                                                     Perfume               Appropriate amount                                      Purified water        Balance                                                 Total                 100.0                                                   (The second agent)                                                            Sodium polyoxyethylene (1.5) alkyl                                                                  10                                                      (12, 14) ether sulfate                                                        Aqueous hydrogen peroxide (30%)                                                                     20                                                      Methylparaben         Appropriate amount                                      Sodium stannate       Appropriate amount                                      Phosphate buffer      Adjusted to pH 3                                        Purified water        Balance                                                 Total                 100                                                     Example 90                                                                    (The first agent)                                                             Undecyl-N-hydroxyethyl-N-                                                                           8.0                                                     carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                 7.0                                                     Myristic acid         4.0                                                     Dimethyl polysiloxane 20 cs                                                                         1.0                                                     Keratin hydrolizate   1.0                                                     Monoethanolamine      2.0                                                     Ammonia water (28%)   10.0                                                    L-ascorbic acid       0.5                                                     Sodium hydrosulfite   0.2                                                     Paraphenylenediamine  1.0                                                     Resorcinol            0.5                                                     Metaaminophenol       0.1                                                     Perfume               Appropriate amount                                      Purified water        Balance                                                 Total                 100.0                                                   (The second agent)                                                            Sodium α-alkenyl (12, 13) sulfonate                                                           8                                                       Sodium polyoxyethylene (1.5) alkyl                                                                  2                                                       (12, 14) ether sulfate                                                        Aqueous hydrogen peroxide (30%)                                                                     20                                                      Methylparaben         Appropriate amount                                      Sodium stannate       Appropriate amount                                      Phosphate buffer      Adjusted to pH 3                                        Purified water        Balance                                                 Total                 100                                                     Example 91                                                                    (The first agent)                                                             Triethanolammonium polyoxyethylene (1.5)                                                            1.0                                                     lauryl ether sulfate                                                          Undecyl-N-hydroxyethyl-N-                                                                           5.0                                                     carboxymethylimidazolinium betaine                                            Sodium Lauroamphoacetate                                                                            5.0                                                     Isostearic acid       3.0                                                     Keratin protein hydrolizate                                                                         1.0                                                     Dimethyl polysiloxane (polymerization                                                               1.5                                                     degree 3,000 to 6,000)                                                        Monoethanolamine      2.0                                                     Ammonia water (28%)   15.0                                                    L-Ascorbic acid       0.5                                                     Thioglycolate salt    1.0                                                     Paraphenylenediamine  1.0                                                     Resorcinol            0.5                                                     Orthoaminophenol      1.0                                                     Perfume               Appropriate amount                                      Purified water        Balance                                                 Total                 100.0                                                   (The second agent)                                                            Sodium α-alkenyl (12, 13) sulfonate                                                           10                                                      Carboxyvinyl polymer ("HivisWako 105",                                                              0.5                                                     produced by Wako Pure Chemical                                                Industries, Ltd.)                                                             Aqueous hydrogen peroxide (30%)                                                                     20                                                      Methylparaben         Appropriate amount                                      Sodium stannate       Appropriate amount                                      Phosphate buffer      Adjusted to pH 3                                        Purified water        Balance                                                 Total                 100                                                     Example 92                                                                    (The first agent)                                                             Undecyl-N-hydroxyethyl-N-                                                                           2.0                                                     carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                 8.0                                                     Oleic acid            3.0                                                     1,3-Butylene glycol   3.0                                                     Collagen protein hydrolizate                                                                        1.0                                                     Monoethanolamine      2.0                                                     Ammonia water (28%)   10.0                                                    L-ascorbic acid       0.5                                                     Paraphenylenediamine  1.0                                                     Resorcinol            1.0                                                     Metaaminophenol       0.5                                                     Perfume               Appropriate amount                                      Purified water        Balance                                                 Total                 100.0                                                   (The second agent)                                                            Sodium polyoxyethylene (1.5) alkyl                                                                  8                                                       (12, 14) ether sulfate                                                        Sodium lauroylmethyltaurate                                                                         2                                                       O- 2-Hydroxy-3-(trimethylammonio)propyl!-                                                           0.5                                                     hydroxyethylcellulose chloride                                                Aqueous hydrogen peroxide (30%)                                                                     20                                                      Methylparaben         Appropriate amount                                      Sodium stannate       Appropriate amount                                      Phosphate buffer      Adjusted to pH 3                                        Purified water        Balance                                                 Total                 100                                                     Example 93                                                                    (The first agent)                                                             Undecyl-N-hydroxyethyl-N-                                                                           4.0                                                     carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                 4.0                                                     Sodium Lauroamphoacetate                                                                            4.0                                                     Isostearic acid       3.0                                                     Keratin protein hydrolizate                                                                         1.0                                                     Amino-modified silicone (produced by                                                                3.0                                                     TORAY INDUSTRIES INC.; SM-8702C)                                              Monoethanolamine      2.0                                                     Ammonia water (28%)   10.0                                                    L-ascorbic acid       0.5                                                     Paraphenylenediamine  1.0                                                     Resorcinol            1.0                                                     Paraaminophenol       0.5                                                     Perfume               Appropriate amount                                      Purified water        Balance                                                 Total                 100.0                                                   (The second agent)                                                            Sodium α-alkenyl (12, 13) sulfonate                                                           12                                                      Sodium lauroylmethyltaurate                                                                         8                                                       O- 2-Hydroxy-3-(trimethylammonio)propyl!-                                                           0.5                                                     hydroxyethylcellulose chloride                                                Aqueous hydrogen peroxide (30%)                                                                     20                                                      Methylparaben         Appropriate amount                                      Sodium stannate       Appropriate amount                                      Phosphate buffer      Adjusted to pH 3                                        Purified water        Balance                                                 Total                 100                                                     Example 94                                                                    (The first agent)                                                             Undecyl-N-hydroxyethyl-N-                                                     carboxymethylimidazolinium betaine                                                                  5.0                                                     Cocoyl Amide Propyldimethyl Glycine                                                                 3.0                                                     Oleic acid            2.0                                                     Liquid paraffin       2.0                                                     Glycerol              4.0                                                     Dimethyl polysiloxane 100 cs                                                                        1.0                                                     Sodium hydroxide      1.0                                                     Ammonia water (28%)   10.0                                                    L-ascorbic acid       0.5                                                     Paraphenylenediamine  1.0                                                     Resorcinol            0.2                                                     Orthoaminophenol      0.8                                                     Perfume               Appropriate amount                                      Purified water        Balance                                                 Total                 100.0                                                   (The second agent)                                                            Sodium polyoxyethylene (1.5) alkyl                                                                  15                                                      (12, 14) ether sulfate                                                        Carboxyvinyl polymer ("HivisWako 105",                                                              0.5                                                     produced by Wako Pure Chemical                                                Industries, Ltd.)                                                             Aqueous hydrogen peroxide (30%)                                                                     20                                                      Methylparaben         Appropriate amount                                      Sodium stannate       Appropriate amount                                      Phosphate buffer      Adjusted to pH 3                                        Purified water        Balance                                                 Total                 100                                                     Example 95                                                                    (The first agent)                                                             Undecyl-N-hydroxyethyl-N-                                                     carboxymethylimidazolinium betaine                                                                  1.0                                                     Cocoyl Amide Propyldimethyl Glycine                                                                 8.0                                                     Isostearic acid       3.0                                                     Quaternized collagen protein hydrolyzate                                                            1.5                                                     Myristic acid         4.0                                                     Dimethyl polysiloxane 6 cs                                                                          2.0                                                     Monoethanolamine      4.0                                                     Ammonia water (28%)   12.0                                                    L-ascorbic acid       0.5                                                     Paraphenylenediamine  0.5                                                     Resorcinol            0.4                                                     Metaaminophenol       0.3                                                     Paraaminoorthocresol  0.2                                                     Perfume               Appropriate amount                                      Purified water        Balance                                                 Total                 100.0                                                   (The second agent)                                                            Sodium α-alkenyl (12, 13) sulfonate                                                           15                                                      Amino-modified silicone (Silicone SM-8702C,                                                         1                                                       produced by TORAY INDUSTRIES INC.)                                            O- 2-Hydroxy-3-(trimethylammonio)propyl!-                                                           0.5                                                     hydroxyethylcellulose chloride                                                Aqueous hydrogen peroxide (30%)                                                                     20                                                      Methylparaben         Appropriate amount                                      Sodium stannate       Appropriate amount                                      Phosphate buffer      Adjusted to pH 3                                        Purified water        Balance                                                 Total                 100                                                     ______________________________________                                    

In the following examples are shown examples of the first agents all ofwhose viscosities became 500 cps when used in combination with thesecond agent of Example 26 or 40, and which exhibited excellentproperties in all of dyeability, dryness to the touch, fadingproperties, low temperature stability and usability.

Example 96

    ______________________________________                                                              (weight %)                                              ______________________________________                                        Sodium polyoxyethylene (1.5) alkyl                                                                    14.0                                                  (12, 14) ether sulfate                                                        Undecyl-N-hydroxyethyl-N-                                                                             2.0                                                   carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                   4.0                                                   Oleic acid              3.0                                                   Keratin protein hydrolyzate                                                                           1.0                                                   Pyrrolidonecarboxylic acid salt                                                                       1.0                                                   Monoethanolamine        2.0                                                   Ammonia water (28%)     10.0                                                  L-ascorbic acid         0.5                                                   Paraphenylenediamine    1.0                                                   Resorcinol              1.0                                                   Metaaminophenol         0.5                                                   Perfume                 Appropriate amount                                    Purified water          Balance                                               Total                   100.0                                                 Example 97                                                                    Sodium polyoxyethylene (1.5) alkyl                                                                    15.0                                                  (12, 14) ether sulfate                                                        Undecyl-N-hydroxyethyl-N-                                                                             2.0                                                   carboxymethylimidazolinium betaine                                            Myristic acid           4.0                                                   Dimethyl polysiloxane 20 cs                                                                           1.0                                                   Keratin protein hydrolyzate                                                                           1.0                                                   Monoethanolamine        3.0                                                   L-ascorbic acid         0.5                                                   Sodium hydrosulfite     0.2                                                   Paraphenylenediamine    1.0                                                   Resorcinol              0.5                                                   Metaaminophenol         0.1                                                   Perfume                 Appropriate amount                                    Purified water          Balance                                               Total                   100.0                                                 Example 98                                                                    Sodium polyoxyethylene (1.5) alkyl                                                                    7.0                                                   (12, 14) ether sulfate                                                        Triethanolammonim polyoxyethylene (1.5)                                                               3.0                                                   lauryl ether sulfate                                                          Undecyl-N-hydroxyethyl-N-                                                                             2.0                                                   carboxymethylimidazolinium betaine                                            Sodium Lauroamphoacetate                                                                              2.0                                                   Isostearic acid         3.0                                                   Keratin protein hydrolyzate                                                                           1.0                                                   Dimethyl polysiloxane (polymerization                                                                 1.5                                                   degree 3,000 to 6,000)                                                        Monoethanolamine        2.0                                                   Ammonia water (28%)     15.0                                                  L-ascorbic acid         0.5                                                   Thioglycolate salt      1.0                                                   Paraphenylenediamine    1.0                                                   Resorcinol              0.5                                                   Orthoaminophenol        1.0                                                   Perfume                 Appropriate amount                                    Purified water          Balance                                               Total                   100.0                                                 Example 99                                                                    Sodium polyoxyethylene (1.5) alkyl                                                                    18.0                                                  (12, 14) ether sulfate                                                        Undecyl-N-hydroxyethyl-N-                                                                             2.0                                                   carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                   1.0                                                   Oleic acid              3.0                                                   1,3-Butylene glycol     3.0                                                   Collagen protein hydrolyzate                                                                          1.0                                                   Monoethanolamine        2.0                                                   Ammonia water (28%)     5.0                                                   L-ascorbic acid         0.5                                                   Paraphenylenediamine    1.0                                                   Resorcinol              1.0                                                   Metaaminophenol         0.5                                                   Perfume                 Appropriate amount                                    Purified water          Balance                                               Total                   100.0                                                 Example 100                                                                   Sodium polyoxyethylene (1.5) alkyl                                                                    25.0                                                  (12, 14) ether sulfate                                                        Undecyl-N-hydroxyethyl-N-                                                                             1.0                                                   carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                   1.0                                                   Sodium Lauroamphoacetate                                                                              1.0                                                   Isostearic acid         3.0                                                   Keratin protein hydrolyzate                                                                           1.0                                                   Amino-modified silicone (SM-8702C;                                                                    3.0                                                   produced by TORAY INDUSTRIES INC.)                                            Monoethanolamine        2.0                                                   Ammonia water (28%)     10.0                                                  L-ascorbic acid         0.5                                                   Paraphenylenediamine    1.0                                                   Resorcinol              1.0                                                   Paraaminophenol         0.5                                                   Perfume                 Appropriate amount                                    Purified water          Balance                                               Total                   100.0                                                 Example 101                                                                   Sodium polyoxyethylene (1.5) alkyl                                                                    25.0                                                  (12, 14) ether sulfate                                                        Oleic acid              2.0                                                   Liquid paraffin         2.0                                                   Glycerol                4.0                                                   Dimethyl polysiloxane 100 cs                                                                          1.0                                                   Sodium hydroxide        1.0                                                   Ammonia water (28%)     10.0                                                  L-ascorbic acid         0.5                                                   Paraphenylenediamine    1.0                                                   Resorcinol              0.2                                                   Orthoaminophenol        0.8                                                   Perfume                 Appropriate amount                                    Purified water          Balance                                               Total                   100.0                                                 Example 102                                                                   Sodium polyoxyethylene (1.5) alkyl                                                                    20.0                                                  (12, 14) etther sulfate                                                       Undecyl-N-hydroxyethyl-N-                                                                             1.0                                                   carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                   3.0                                                   Isostearic acid         3.0                                                   Quaternized collagen protein hydrolyzate                                                              1.5                                                   Dimethyl polysiloxane 6 cs                                                                            2.0                                                   Monoethanolamine        4.0                                                   Ammonia water (28%)     12.0                                                  L-ascorbic acid         0.5                                                   Paraphenylenediamine    0.5                                                   Resorcinol              0.4                                                   Metaaminophenol         0.3                                                   Paraaminoorthocresol    0.2                                                   Perfume                 Appropriate amount                                    Purified water          Balance                                               Total                   100.0                                                 Example 103                                                                   Sodium polyoxyethylene (1.5) alkyl                                                                    15.0                                                  (12, 14) ether sulfate                                                        Undecyl-N-hydroxyethyl-N-                                                                             8.0                                                   carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                   7.0                                                   Myristic acid           4.0                                                   Dimethyl polysiloxane 20 cs                                                                           1.0                                                   Keratin hydrolyzate     1.0                                                   Monoethanolamine        4.0                                                   Ammonia water (28%)     10.0                                                  L-ascorbic acid         0.5                                                   Paraphenylenediamine    1.0                                                   Resorcinol              0.5                                                   Metaaminophenol         0.1                                                   Perfume                 Appropriate amount                                    Purified water          Balance                                               Total                   100.0                                                 Example 104                                                                   Sodium polyoxyethylene (1.5) alkyl                                                                    6.0                                                   (12, 14) ether sulfate                                                        Triethanolammonium polyoxyethylene (1.5)                                                              4.0                                                   lauryl ether sulfate                                                          Undecyl-N-hydroxyethyl-N-                                                                             5.0                                                   carboxymethylimidazolinium betaine                                            Sodium Lauroamphoacetate                                                                              5.0                                                   Isostearic acid         3.0                                                   Keratin protein hydrolyzate                                                                           1.0                                                   Dimethyl polysiloxane (polymerization                                                                 1.5                                                   degree 3,000 to 6,000)                                                        Monoethanolamine        2.0                                                   Ammonia water (28%)     15.0                                                  L-ascorbic acid         0.5                                                   Thioglycolate salt      1.0                                                   Paraphenylenediamine    1.0                                                   Resorcinol              0.5                                                   Orhtoaminophenol        1.0                                                   Perfume                 Appropriate amount                                    Purified water          Balance                                               Total                   100.0                                                 Example 105                                                                   Sodium polyoxyethylene (1.5) alkyl                                                                    5.0                                                   (12, 14) ether sulfate                                                        Sodium lauroylmethyltaurate                                                                           5.0                                                   Undecyl-N-hydroxyethyl-N-                                                                             2.0                                                   carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                   8.0                                                   Oleic acid              3.0                                                   1,3-Butylene glycol     3.0                                                   Collagen protein hydrolyzate                                                                          1.0                                                   Monoethanolamine        2.0                                                   Ammonia water (28%)     10.0                                                  L-ascorbic acid         0.5                                                   Paraphenylenediamine    1.0                                                   Resorcinol              1.0                                                   Metaaminophenol         0.5                                                   Perfume                 Appropriate amount                                    Purified water          Balance                                               Total                   100.0                                                 Example 106                                                                   Sodium polyoxyethylene (1.5) alkyl                                                                    8.0                                                   (12, 14) ether sulfate                                                        Undecyl-N-hydroxyethyl-N-                                                                             4.0                                                   carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                   4.0                                                   Sodium Lauroamphoacetate                                                                              4.0                                                   Isostearic acid         3.0                                                   Keratin protein hydrolyzate                                                                           1.0                                                   Amino-modified silicone (SM-8702C; produced                                                           3.0                                                   by TORAY INDUSTRIES INC.)                                                     Monoethanolamine        2.0                                                   Ammonia water (28%)     10.0                                                  L-ascorbic acid         0.5                                                   Paraphenylenediamine    1.0                                                   Resorcinol              1.0                                                   Paraaminophenol         0.5                                                   Perfume                 Appropriate amount                                    Purified water          Balance                                               Total                   100.0                                                 Example 107                                                                   Sodium polyoxyethylene (1.5) alkyl                                                                    12.0                                                  (12, 14) ether sulfate                                                        Undecyl-N-hydroxyethyl-N-                                                                             5.0                                                   carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                   3.0                                                   Oleic acid              2.0                                                   Liquid paraffin         2.0                                                   Glycerol                2.0                                                   Dimethyl polysiloxane 100 cs                                                                          1.0                                                   Sodium hydroxide        1.0                                                   Ammonia water (28%)     10.0                                                  L-ascorbic acid         0.5                                                   Paraphenylenediamine    1.0                                                   Resorcinol              0.2                                                   Orthoaminophenol        0.8                                                   Perfume                 Appropriate amount                                    Purified water          Balance                                               Total                   100.0                                                 ______________________________________                                    

In the following examples, hair-bleaching agent (decoloring agent)compositions of the invention are specifically described in comparisonwith comparative examples.

Evaluation of the compositions of the invention was conducted accordingto the following criteria.

1) Decolorization effect test using hair strands Untreated hair strands(2 g) were coated with 10 g of a decoloring agent, and evaluation wasmade from the relations between time for which the hair strans were leftalone and the L value. The L value means the value of L in the colordifference equation of Hunter.

2) Comparative test on decolorization effect and dryness to the touch bya panel of experts

A series of decolorization operations was conducted, and decolorizationeffect of the hair of the head and dryness to the touch after dryingwere evaluated according to the following criterion, using a panel of 10experts.

<Decolorization effect>

++ . . . Decolorization effect is remarkably good and the hair isuniformly decolorized

+ . . . Decolorization effect is good and the hair is uniformlydecolorized

± . . . Decolorization effect is a little poor

- . . . The hair is unevenly decolorized and decolorization effect islow

<Dryness to the touch>

++ . . . The hair is not dry to the touch and gives smooth touch

+ . . . The hair is not dry to the touch

± . . . The hair is a little dry to the touch

- . . . The hair is remarkably dry to the touch

3) Viscosity of mixed solution

The first agent and the second agent were mixed and the viscosity of themixed solution was measured at 30° C. using a Brook-field typeviscometer.

4) Low temperature stability

The first agent (100 g) was stored in a constant temperature bath of -5°C. for one month, and the state thereof was visually observed andevaluated according to the following criterion.

++ . . . Any change is not observed at all compared with the initialstate

+ . . . Any change is not observed at all compared with the initialstate, but there is a slight increase of the viscosity

± . . . A slight turbidity is formed

- . . . Separation occurs

Example 108 and Comparative Example 51 (Usual System)

The following first agent and the second agent of the invention or ausual system were mixed in a ratio of 1:1 to prepare a hair-bleachingagent, and using black hair strands, the difference in decolorizationeffect between the invention and the usual system was evaluated based onrelations between time for which the black hair strands were left aloneand the L value, according to the above-mentioned method.

Further, the viscosities of the first agent and the second agent, andthe viscosity after mixing of both were measured.

    ______________________________________                                                           (weight %)                                                 ______________________________________                                        Example 108                                                                   (The first agent)                                                             Undecyl-N-hydroxyethyl-N-                                                                          3.0                                                      carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                7.0                                                      Oleic acid           3.0                                                      Monoethanolamine     2.0                                                      Ammonia water (28%)  10.0                                                     Perfume              Appropriate amount                                       Purified water       Balance                                                  Total                100.0                                                    (The second agent)                                                            Sodium Polyoxyethylene (1.5) alkyl                                                                 10.0                                                     (12, 14) ether sulfate                                                        Aqueous hydrogen peroxide                                                                          20.0                                                     Methylparaben        Appropriate amount                                       Sodium stannate      Appropriate amount                                       Phosphate buffer     Adjusted to pH 3                                         Purified water       Balance                                                  Total                100.0                                                    Comparative example 51                                                        (The first agent)                                                             Polyoxyethylene (2) oleyl ether                                                                    15.0                                                     Polyoxyethylene (5) octylphenyl ether                                                              5.0                                                      Oleic acid           10.0                                                     Monoethanolamine     2.0                                                      Ammonia water (28%)  10.0                                                     Perfume              Appropriate amount                                       Purified water       Balance                                                  Total                100.0                                                    (The second agent)                                                            Aqueous hydrogen peroxide (30%)                                                                    20.0                                                     Methylparaben        Appropriate amount                                       Sodium stannate      Appropriate amount                                       Phosphate buffer     Adjusted to pH 3                                         Purified water       Balance                                                  Total                100.0                                                    ______________________________________                                    

As to the first agent of Example 108, the pH was 10.58 and the viscositywas 120 cps, and as to the second agent, the pH was 3.0 and theviscosity was 12 cps, and after both were mixed, the pH became 9.2 andthe viscosity became 3,800 cps, and remarkable thickening effect wasobserved.

Next, the first agent and the second agent of Example 108 were used, andan appropriate amount of a pH-adjusting agent (ammonia water orphosphoric acid) was added at the time of mixing to prepare decoloringagents of pH 5, 6 and 12, respectively. When viscosity was measured, theviscosities of these decoloring agents were 480 cps, 3,020 cps and 1,050cps, respectively, and it was found that in the decoloring agentswherein the pH was made to be 6 to 12, excellent thickening effect canbe obtained. Further, the ΔL values at 20 minutes after thedecolorization treatment were 5, 18 and 32, respectively, and it wasrevealed that decolorization effect is high in the range of pH 6 to 12.

Example 109 and Comparative examples 52 and 53 (Usual System)

The following first agent and the second agent of the invention or ausual system were mixed in a ratio of 1:1 to prepare a hair-bleachingagent, and using black hair strands, the difference in decolorizationeffect between the invention and the usual system was evaluated based onrelations between time for which the black hair strands were left aloneand the L value.

Further, the viscosities of the first agent and the second agent, andthe viscosity after mixing of both were measured.

    ______________________________________                                                             (weight %)                                               ______________________________________                                         The first agent! (Prescription 1-A)                                          Sodium Polyoxyethylene (1.5) alkyl                                                                   10.0                                                   (12, 14) ether sulfate                                                        Undecyl-N-hydroxyethyl-N-                                                                            5.0                                                    carboxymethylimidazolinium betaine                                            Cocoyl Amide Propyldimethyl Glycine                                                                  5.0                                                    Oleic acid             3.0                                                    Propylene glycol       5.0                                                    Monoethanolamine       2.0                                                    Ammonia water (28%)    10.0                                                   Purified water         Balance                                                Total                  100.0                                                   The first agent! (Prescription 1-B)                                          Polyoxyethylene (3) oleyl ether                                                                      15.0                                                   Polyoxyethylene (4) octylphenyl ether                                                                5.0                                                    Ethanol                10.0                                                   Monoethanolamine       2.0                                                    Ammonia water (28%)    5.0                                                    Purified water         Balance                                                Total                  100.0                                                   The second agent! (Prescription 2-A)                                         Aqueous hydrogen peroxide (30%)                                                                      20.0                                                   Methylparaben          0.1                                                    Sodium stannate        0.1                                                    O- 2-hydroxy-3-(trimethylammoniapropyl!-                                                             1.0                                                    hydroxycellulose  Polymer JR-400 (produced                                    by Union Carbide Co.)!                                                        Phosphate buffer       Adjusted to pH 2                                       Purified water         Balance                                                Total                  100.0                                                   The second agent! (Prescription 2-B)                                         Aqueous hydrogen peroxide (30%)                                                                      20.0                                                   Methylparaben          0.1                                                    Sodium stannate        0.1                                                    Phosphate buffer       Adjusted to pH 2                                       Purified water         Balance                                                Total                  100.0                                                  ______________________________________                                                               Comparative                                                                              Comparative                                             Example 109                                                                              example 52 example 53                                  ______________________________________                                        The first agent                                                                           Prescription                                                                             Prescription                                                                             Prescription                                            1-A        1-B        1-A                                         The second agent                                                                          Prescription                                                                             Prescription                                                                             Prescription                                            2-A        2-B        2-B                                         Viscosity of the                                                                            170      70         170                                         first agent                                                                   Viscosity of the                                                                            40       40          15                                         second agent                                                                  Viscosity at the                                                                          3,200      2,500      460                                         time of mixing                                                                Dyeability  ++         ±       ++                                          Dryness to the touch                                                                      ++         -          ++                                          Low temperature                                                                           ++         +          ++                                          stability                                                                     ______________________________________                                    

As to the first agent of Example 109, the pH was 11.0and the viscositywas 170cps, and as to the second agent, the pH was 2.0 and the viscositywas 40 cps, and after both were mixed, the pH became 9.4 and theviscosity became 3,200 cps, and remarkable thickening effect wasobserved.

Next, the first agent and the second agent of Example 109 were used, andan appropriate amount of a pH-adjusting agent (ammonia water orphosphoric acid) was added at the time of mixing to preparehair-bleaching agents of pH 5, 6 and 12, respectively. When viscositywas measured, the viscosities of these hairbleaching agents were 330cps, 1,600 cps and 800 cps, respectively, and it was found that in thehair-bleaching agents wherein the pH was made to be 6 to 12 , excellentthickening effect can be obtained. Further, the ΔL values at 20 minutesafter the decolorization treatment were 4, 18 and 30, respectively, andit was revealed that decolorization effect is high in the range of pH 6to 12.

Examples 110 to 157 and Comparative Examples 54 to 69

The first agents and the second agents of various compositions shown inTable 21 to Table 28 were mixed to prepare hair-bleaching agents,respectively, and these hair-bleaching agents were evaluated accordingto the above-mentioned evaluation methods. All the pH values of thehair-bleaching agents in Table 1 to Table 3 were 6 to 12.

                                      TABLE 21                                    __________________________________________________________________________                     Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    110  111  112  113  114  115  116  117                       __________________________________________________________________________    (The first agent)                                                             Undecyl-N-hydroxy-N-carboxy-                                                                   8    --   2    3    4    8    15   4                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            --   --   8    12   --   7    3      2.66                    Sodium Lauroamphoacetate                                                                       --   --   --   --   6    --   --                             Oleic acid       2    3    3    3    3    3    4    2                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   --                        product)                                                                      Monoethanolamine 1    2    2    2    2    2    2    1                         Ammonia water (28%)                                                                            10   15   10   15   10   15   15   10                        Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            Triethanolammonium polyoxyethylene                                                             8    10   15   10   10   10   9    15                        (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       --   --   --   --   --   --   --   --                        Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   --   --   --                        O- 2-hydroxy-3-(trimethylammonio)-                                                             --   --   --   --   --   --   --   --                        propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                  --   --   --   --   --   --   --   --                        polychloride                                                                  Dimethylallyammonium chloride                                                                  --   --   --   --   --   --   --   --                        acrylamide copolymer                                                          Vinyl pyrrolidone-N,N--                                                                        --   --   --   --   --   --   --   --                        dimethylaminoethyl methacrylate--                                             stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1    1/1.5                                                                            1/2  1.5/1                     second agent)                                                                 Weight ratio (anionic surface active                                                           5/5  10/0 6/4  4/6  5/5  5/5  5/5  4/6                       agent/amphoteric surface active agent)                                        pH at the time of mixing                                                                         9.4                                                                                9.8                                                                              9      9.4                                                                                9.1                                                                                9.1                                                                                8.9                                                                                9.4                     Decolorization effect                                                                          ++   ++   ++   ++   ++   ++   +    ++                        Dryness to the touch                                                                           ++   ++   ++   ++   ++   ++   ++   ++                        Viscosity of the first agent                                                                   120  140  120  180  140  140  170  130                       Viscosity of the second agent                                                                  40   40   40   55   45   50   45   40                        Viscosity after mixing                                                                         3500 3500 5500 2900 4200 2200 2600 1900                      Low temperature stability                                                                      ++   ++   ++   ++   ++   ++   ++   ++                        __________________________________________________________________________

                                      TABLE 22                                    __________________________________________________________________________                     Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    115  119  120  121  122  123  124  125                       __________________________________________________________________________    (The first agent)                                                             Undecyl-N-hydroxy-N-carboxy-                                                                   2    1    2    2    2    5    4    6                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            6    9    6    4    10   10   6    6                         Sodium Lauroamphoacetate                                                                       --   --   --   2    --   --   --   --                        Oleic acid       2    3    3    3    3    3    3    2                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   1                         product)                                                                      Monoethanolamine 1    2    2    2    2    2      7.0                                                                                6.0                     Ammonia water (28%)                                                                            10   10   10   10   12   10   --   --                        1 ,3-Butylene Glycol                                                                           2    1    3    2      1.5                                                                              2      4.5                                                                              4                         Ethanol          --   --   --   --   --   2    --   --                        Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            Triethanolammonium polyoxyethylene                                                             8    10   10   --   --   --   5    5                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       --   --   2    8    8    10   --   3                         Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   --   5    --                        O- 2-hydroxy-3-(trimethylammonio)-                                                             --   --     0.5                                                                              --   --   --   --   --                        propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                    0.5                                                                              --   --   --   --   --   --   --                        polychloride                                                                  Dimethylallyammonium chloride                                                                  --   --   --     0.3                                                                              --   --   --   --                        acrylamide copolymer                                                          Vinylpyrrolidone-N,N-                                                                          --   --   --   --   --   --     0.5                                                                              --                        dimethylaminoethyl methacrylate-                                              stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1    1/1.5                                                                            1/1  1/1                       second agent)                                                                 Weight ratio (anionic surface active                                                           5/5  5/5  6/4  5/5  6/4  5/5  5/5  6/4                       agent/amphoteric surface active agent)                                        pH at the time of mixing                                                                         9.4                                                                                9.3                                                                                9.1                                                                                9.2                                                                                9.4                                                                                9.3                                                                                9.1                                                                                8.9                     Decolorization effect                                                                          ++   ++   ++   ++   ++   ++   +    +                         Dryness to the touch                                                                           ++   ++   ++   ++   ++   ++   ++   ++                        Viscosity of the first agent                                                                   120  140  140  90   150  120  160  180                       Viscosity of the second agent                                                                  40   40   40   30   40   30   40   40                        Viscosity after mixing                                                                         3500 5800 7200 4600 4400 2800 3800 4800                      Low temperature stability                                                                      ++   ++   ++   ++   ++   ++   ++   ++                        __________________________________________________________________________

                                      TABLE 23                                    __________________________________________________________________________                     Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    126  127  128  129  130  131  132  133                       __________________________________________________________________________    (The first agent)                                                             Undecyl-N-hydroxy-N-carboxy-                                                                   2    2    2    2    1    5    5    2                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            6    --   8    2    4    2    11   8                         Sodium Lauroamphoacetate                                                                       --   --   --   --   --   3    --   --                        Oleic acid       3    3    3    3    3    3    3    2                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   --                        product)                                                                      Monoethanolamine 1    2    2    2    2    2    2    1                         Ammonia water (28%)                                                                            15   10   8    10   10   10   11   6                         1,3-Butylene glycol                                                                            1    0.5  3    1    0.5  2    0.5  2.5                       Ethanol          --   --   --   --   --   --   --   0.5                       Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            Triethanolammonium polyoxyethylene                                                             2    --   8    4    1    6    --   5                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       8    18   2    12   4    --   10   5                         Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   4    --   --                        O- 2-hydroxy-3-(trimethylammonio)-                                                             --   --   --   --   --   --   --   --                        propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                  --   --   --   --   --   --   --   --                        polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --   --   --   --   --   --                        acrylamide copolymer                                                          Vinyl pyrrolidone-N,N-                                                                         --   --   --   --   --   --   --   --                        dimethylaminoethyl methacrylate-                                              stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1  1/1    1/1.5                                                                            1/1                       second agent)                                                                 Weight ratio (anionic surface active                                                           5/5  9/1  6/4  8/2  5/5  5/5  5/5  5/5                       agent/amphoteric surface active agent)                                        pH at the time of mixing                                                                       11.4 9.1  8.8  9.3  9.1  9.1  9.4  8.9                       Decolorization effect                                                                          ++   ++   +    ++   ++   ++   ++   ++                        Dryness to the touch                                                                           +    ++   ++   ++   ++   ++   ++   ++                        Viscosity of the first agent                                                                   100  80   160  90   90   110  190  150                       Viscosity of the second agent                                                                  30   40   45   35   20   30   40   40                        Viscosity after mixing                                                                         1500 3700 6200 3000 650  900  4600 5900                      Low temperature stability                                                                      ++   ++   ++   ++   ++   ++   ++   ++                        __________________________________________________________________________

                                      TABLE 24                                    __________________________________________________________________________                     Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    134  135  136  137  138  139  140  141                       __________________________________________________________________________    (The first agent)                                                             Triethanolammonium polyoxyethylene                                                             8    10   15   10   10   10   10   8                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       --   --   --   --   --   --   --   --                        Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   --   --   --                        Undecyl-N-hydroxy-N-carboxy-                                                                   8    --   2    3    4    3    5    4                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            --   --   8    12   --   7    5    8                         Sodium Lauroamphoacetate                                                                       --   --   --   --   6    --   --   --                        Oleic acid       2    3    3    3    3    3    4    2                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   --                        product)                                                                      Monoethanolamine 1    2    2    2    2    2    2    1                         Ammonia water (28%)                                                                            1    15   10   15   10   15   15   10                        Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            O- 2-hydroxy-3-(trimethylammonio)-                                                             0.1  0.5  --   --   --   0.5  0.2  --                        propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                  --   --   0.5  --   --   --   --   --                        polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --   0.5  --   --   --   0.2                       acrylamide copolymer                                                          Vinylpyrrolidone-N,N-                                                         dimethylaminoethyl methacrylate-                                                               --   --   --   --   0.5  --   0.5  --                        stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1    1/1.5                                                                            1/2  1.5/1                     second agent)                                                                 Weight ratio (anionic surface                                                                  5/5  10/0 6/4  4/6  5/5  5/5  5/5  4/6                       active agent/amphoteric surface                                               active agent)                                                                 pH at the time of mixing                                                                       9.5  9.8  9.2  9.5  9.2  9.2  9    9.4                       Decolorization effect                                                                          ++   ++   ++   ++   ++   ++   ++   ++                        Dryness to the touch                                                                           ++   ++   ++   ++   ++   ++   ++   ++                        Viscosity of the first agent                                                                   150  130  140  160  160  140  150  120                       Viscosity of the second agent                                                                  10   10   10   5    15   10   10   10                        Viscosity after mixing                                                                         3500 1800 4500 2800 1700 1500 850  1700                      Low temperature stability                                                                      ++   ++   ++   ++   ++   ++   ++   ++                        __________________________________________________________________________

                                      TABLE 25                                    __________________________________________________________________________                     Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    142  143  144  145  146  147  148  149                       __________________________________________________________________________    (The first agent)                                                             Triethanolammonium polyoxyethylene                                                             8    10   10   --   --   --   5    5                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       --   --   2    8    8    15   --   3                         Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   --   5    --                        Undecyl-N-hydroxy-N-carboxy-                                                                   2    1    2    2    2    5    4    6                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            6    9    6    4    10   10   6                              Sodium Lauroamphoacetate                                                                       --   --   --   2    --   --   --   --                        Oleic acid       2    3    3    3    3    3    3    2                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   1                         product)                                                                      Monoethanolamine 1    2    2    2    2    2    6.5  7.0                       Ammonia water (28%)                                                                            10   10   10   10   12   10   --   --                        1,3-Butylene glycol                                                                            2    1    3    2    1.5  2    2.0  1.0                       Ethanol          --   --   --   --   --   2    --   --                        Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            O- 2-hydroxy-3-(trimethylammonio)-                                                             --   0.1  0.5  --   0.1  --   --   2                         propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                  0.5  --   --   --   --   0.5  --   --                        polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --   0.3  0.1  --   --   --                        acrylamide copolymer                                                          Vinyl pyrrolidone-N,N-                                                                         --   --   --   --   --   --   0.5  --                        dimethylaminoethyl methacrylate-                                              stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1    1/1.5                                                                            1/1  1/1                       second agent)                                                                 Weight ratio (anionic surface active                                                           5/5  5/5  6/4  5/5  6/4  5/5  5/5  6/4                       agent/amphoteric surface active agent)                                        pH at the time of mixing                                                                       9.4  9.3  9.1  9.4  9.2  9.3  9.0  9.2                       Decolorization effect                                                                          ++   ++   ++   ++   ++   ++   ++   ++                        Dryness to the touch                                                                           ++   ++   ++   ++   ++   ++   ++   ++                        Viscosity of the first agent                                                                   120  150  120  90   140  130  170  180                       Viscosity of the second agent                                                                  10   10   10   10   5    10   15   10                        Viscosity after mixing                                                                         2500 4800 4600 2000 2800 1800 750  1200                      Low temperature stability                                                                      ++   ++   ++   ++   ++   ++   ++   ++                        __________________________________________________________________________

                                      TABLE 26                                    __________________________________________________________________________                     Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    150  151  152  153  154  155  156  157                       __________________________________________________________________________    (The first agent)                                                             Triethanolammonium polyoxyethylene                                                             2    --   8    4    1    6    --   5                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       8    18   2    12   4    --   10   5                         Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   4    --   --                        Undecyl-N-hydroxy-N-carboxy-                                                                   2    2    2    2    1    5    5    2                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            6    --   8    2    4    2    5    8                         Sodium Lauroamphoacetate                                                                       --   --   --   --   --   3    --   --                        Oleic acid       3    3    3    3    3    3    3    2                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   --                        product)                                                                      Monoethanolamine 1    2    2    2    2    2    2    1                         Ammonia water (28%)                                                                            15   10   8    10   10   10   11   6                         1,3-Butylene glycol                                                                            1    0.5  3    1    0.5  2    0.5  2.5                       Ethanol          --   --   --   --   --   --   --   0.5                       Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            O- 2-hydroxy-3-(trimethylammonio)-                                                             0.5  4    5    2    0.01 0.2  0.5  0.5                       propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                  --   --   --   --   --   --   --   --                        polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --   --   --   --   --   0.1                       acrylamide copolymer                                                          Vinyl pyrrolidone-N,N-                                                                         --   --   --   --   --   --   0.5  --                        dimethylaminoethyl methacrylate-                                              stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1  1/1    1/1.5                                                                            1/1                       second agent)                                                                 Weight ratio (anionic surface active                                                           5/5  9/1  6/4  8/2  5/5  5/5  5/5  5/5                       agent/amphoteric surface active agent)                                        pH at the time of mixing                                                                       11.4 9.1  8.8  9.3  9.2  9.1  9.3  9                         Decolorization effect                                                                          ++   ++   +    ++   ++   ++   ++   ++                        Dryness to the touch                                                                           +    ++   ++   ++   ++   ++   ++   ++                        Viscosity of the first agent                                                                   90   60   60   80   70   100  180  120                       Viscosity of the second agent                                                                  10   10   10   5    10   15   10                             Viscosity after mixing                                                                         1800 1500 2200 5100 1600 2100 4150 1500                      Low temperature stability                                                                      ++   ++   ++   ++   ++   ++   ++   ++                        __________________________________________________________________________

                                      TABLE 27                                    __________________________________________________________________________                     Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                   tive tive tive tive tive tive tive tive                                       Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    54   55   56   57   58   59   60   61                        __________________________________________________________________________    (The first agent)                                                             Undecyl-N-hydroxy-N-carboxy-                                                                   14        7         5    10   2    6                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            --   14   --        5         6    6                         Sodium Lauroamphoacetate                                                                       --   13   --   --   --   --   --   --                        Oleic acid       2    3    3         3    3         2                         Sodium polyoxyethylene (1.5) alkyl                                                             --                                                           (12,14) ether sulfate                                                         Polyoxyethylene (2) oleyl ether                                                                --        5    5         5                                   Polyoxyethylene (5) octylphenyl ether                                                          --                       5                                   Sodium alkylbenzenesulfonate                                                                   --                                 5                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   1                              product)                                                                      Monoethanolamine 1    2    2    2    2    2    2    3                         Ammonia water (28%)                                                                            10   10   10   10   12   10   10   10                        1,3-Butylene glycol                                                                            --   --   --                                                 Ethanol          --                                 10                        Isopropanol      8                                                            Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            Triethanolammonium polyoxyethylene                                                             6    6    3    10   --   --   8    5                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       --   --   --   --   --   --   --   3                         Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   --   --   --                        O- 2-hydroxy-3-(trimethylammonio)-                                            propyl!hydroxyethylcellulose                                                                   --   --   --   --   --   --   --   --                        chloride                                                                      Dimethylmethylenepiperidinium                                                                  --   --   --   --   --   --   --   --                        polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --   --   --   --   --   --                        acrylamide copolymer                                                          Vinylpyrrolidone-N,N-                                                         dimethylaminoethyl methacrylate-                                                               --   --   --   --   --   --   --   --                        stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                   Aqueous hydrogen peroxide (30%)                                                                20   20   20   20   20   20   20   20                        Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1  1/1  1/1  1/1                       second agent)                                                                 Weight ratio (anionic surface                                                                  3/7  3/7  3/7  10/0  0/10                                                                               0/10                                                                              5/5  4/6                       active agent/amphoteric surface                                               active agent)                                                                 pH at the time of mixing                                                                       9.3  9.4  9.2  9.5  9.7  9.3  9.7  9.6                       Decolorization effect                                                                          ++   ++   ++   ++   ++   ++   ++   ++                        Dryness to the touch                                                                           ++   -    ± ± ++   -    +    -                         Viscosity of the first agent                                                                   100  120  130  100  110  100  110  50                        Viscosity of the second agent                                                                  60   90   40   30   20   20   20   30                        Viscosity after mixing                                                                         250  400  1100 1400 250  1300 1400 420                       Low temperature stability                                                                      ++   ++   ± ± +    ± -    +                         __________________________________________________________________________

                                      TABLE 28                                    __________________________________________________________________________                     Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                                                           Compara-                                   tive tive tive tive tive tive tive tive                                       Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                                                            Example                                    62   63   64   65   66   67   68   69                        __________________________________________________________________________    (The first agent)                                                             Triethanolammonium polyoxyethylene                                                             6    6    3    10   --   --   8    5                         (2) alkyl (12,14) ether sulfate                                               Sodium α-alkenyl (12,13) sulfonate                                                       --   --                       --   3                         Sodium lauroylmethyltaurate                                                                    --   --   --   --   --   --   --   --                        Undecyl-N-hydroxy-N-carboxy-                                                                   14        7         5    10   2    6                         methylimidazolinium betaine                                                   Cocoyl Amide Propyldimethyl Glycine                                                            --   14   --        5         6    6                         Sodium Lauroamphoacetate                                                                       --   --   --        --   --   --   --                        Oleic acid       2    3    3         3    3         2                         Polyoxyethylene (2) oleyl ether                                                                --        5    5         5                                   Polyoxyethylene (5) octylphenyl ether                                                          --                       5                                   sodium alkylbenzenesulfonate                                                                   --                                 5                         Isostearic acid (Emery #871 desalted                                                           --   --   --   --   --   --   --   1                         product)                                                                      Monoethanolamine 1    2    2    2    2    2    2    3                         Ammonia water (28%)                                                                            10   10   10   10   12   10   10   10                        1,3-Butylene glycol                                                                            --   --   --                                                 Ethanol          --                                 10                        Isopropanol      8                             8                              Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    (The second agent)                                                            O- 2-hydroxy-3-(trimethylammonio)-                                                             0.5  0.5  --   0.2  0.5  --   0.2  0.2                       propyl!hydroxyethylcellulose                                                  chloride                                                                      Dimethylmethylenepiperidinium                                                                  --   --   0.5  --   --   0.5  --   --                        polychloride                                                                  Dimethylallyammonium chloride-                                                                 --   --   --   --   --   --   --   --                        acrylamide copolymer                                                          Vinyl pyrrolidone-N,N-                                                                         --   --   --   0.1  --   --   --   --                        dimethylaminoethyl methacrylate-                                              stearyl acrylate-tripropylene                                                 glycol diacrylate copolymer                                                                    20   20   20   20   20   20   20   20                        Aqueous hydrogen peroxide (30%)                                               Sodium stannate  Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Methylparaben    Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                                                            Approp-                                    riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                                                              riate                                      amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                                                                             amount                    Phosphate buffer Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                                                           Adjusted                                   to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                                                                            to pH 3                   Purified water   to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                                                                             to 100                    Mixing ratio (the first agent/the                                                              1/1  1/1  1/1  1/1  1/1  1/1  1/1  1/1                       second agent)                                                                 Weight ratio (anionic surface active                                                           3/7  3/7  3/7  10/0  0/10                                                                               0/10                                                                              5/5  4/6                       agent/amphoteric surface active agent)                                        pH at the time of mixing                                                                       9.3  9.4  9.2  9.6  9.7  9.1  9.6  9.5                       Decoloration effect                                                                            ++   ++   ++   ++   ++   ++   ++   +                         Dryness to the touch                                                                           ++   -    ± ± ++   -    -    -                         Viscosity of the first agent                                                                   150  140  110  80   130  100  150  50                        Viscosity of the second agent                                                                  40   40   30   30   20   30   20   20                        Viscosity after mixing                                                                         220  350  1000 1400 200  1500 250  400                       Low temperature stability                                                                      ++   ++   ± ± +    ± -    +                         __________________________________________________________________________

From the results shown in Table 21 to Table 28, it is seen that thehair-bleaching agents of the invention are excellent in decolorizationeffect, free from dryness to the touch, low in viscosity on the firstagents and the second agents, moderate in the viscosity after mixing andmoreover excellent in low temperature stability. Further, in the usualhair dyes, for making the first agent low viscous and obtaining highviscosity at the time of mixing with the second agent, as shown inComparative example 52, the nonionic surface active agent is compoundedin a high concentration and the monohydric alcohol (isopropanol) isadded so that the viscosity can be lowered, and heightened at the timeof mixing, whereas in the invention, it is possible to make the firstagent low viscous without incorporating a monohydric alcohol and attainhigh viscosity at the time of mixing.

As further hair-bleaching agent compositions of the invention, there canbe mentioned ones obtained by merely removing the dyes (compoundsrelating to the dyeing system) from the compositions of Examples 89 to107 or substituting alkalinizing agents for the dyes. Any of them alsoexhibited the desired effects of the invention.

Industrially Applicable Field

According to the invention, a novel mixing-at the time of use-typehair-treating agent is provided. Such a composition is used for dyeinghair or bleaching hair, and particularly, the preparations before useare relatively low viscous and have stable physical properties, but whenthey are mixed at the time of use, the mixture exhibits such a viscositythat dropping from the hair becomes zero or is reduced (thickening), andmoreover it exhibits excellent dyeing effect or bleaching effect.

Therefore, the invention can be advantageously utilized in the field ofpreparation of cosmetics.

We claim:
 1. A mixing-at the time of use-type hair dye compositionwherein a dye and an oxidizing agent are combined at the time of use,wherein(a) the composition after the combination comprises a dye (I),one or more (II) of surface active agents selected from the groupconsisting of amphoteric surface active agents and semipolar surfaceactive agents, (II) being optional component(s), one or more (III) ofhigher fatty acids, one or more (IV) of anionic surface active agents,an oxidizing agent (V), and water (VII), and (b) before use, componentsselected from the group consisting of components (I), (II) and (III) areput in such a form that they each are separated from component (V).
 2. Amixing-at the time of use-type hair-bleaching agent composition whereinan alkalinizing agent and an oxidizing agent are combined at the time ofuse, wherein(a) the composition after the combination comprises analkalinizing agent (I'), one or more (II) of surface active agentsselected from the group consisting of amphoteric surface active agentsand semipolar surface active agents, (II) being optional component(s),one or more (III) of higher fatty acids, one or more (IV) of anionicsurface active agents, an oxidizing agent (V), and water (VII), and (b)before use, components selected from the group consisting of components(I'), (II) and (III) are put in such a form that they each are separatedfrom component (V).
 3. The composition according to claim 1 or 2 whereinin (b), component (IV) is put in such a form that it is mixed withcomponents (I) or (I'), (II), (III) and (VII).
 4. The compositionaccording to claim 1 or 2 wherein in (b), component (IV) is put in sucha form that it is mixed with components (I) or (I'), (II), (III) and(VII), and it is also mixed with components (V) and (VII).
 5. Thecomposition according to claim 1 or 2 wherein in (b), component (IV) isput in such a form that it is mixed with components (V) and (VII).
 6. Amixing-at the time of use-type hair dye composition wherein a dye and anoxidizing agent are combined at the time of use, wherein(a) thecomposition after the combination comprises a dye (I), one or more (II)of surface active agents selected from the group consisting ofamphoteric surface active agents and semipolar surface active agents,(II) being optional component(s), one or more (III) of higher fattyacids, one or more (IV) of anionic surface active agents, an oxidizingagent (V), a cationic polymer (VI) and water (VII), and (b) before use,components selected from the group consisting of components (I), (II),(III) and (IV) are put in such a form that they are separated fromcomponents selected from the group consisting of components (V) and(VI).
 7. A mixing-at the time of use-type hair-bleaching agentcomposition wherein an alkalinizing agent and an oxidizing agent arecombined at the time of use, wherein(a) the composition after thecombination comprises an alkalinizing agent (I'), one or more (II) ofsurface active agents selected from the group consisting of amphotericsurface active agents and semipolar surface active agents, (II) beingoptional component(s), one or more (III) of higher fatty acids, one ormore (IV) of anionic surface active agents, an oxidizing agent (V), acationic polymer (VI) and water (VII), and (b) before use, componentsselected from the group consisting of components (I'), (II), (III) and(IV) are put in a form separated from components selected from the groupconsisting of components (V) and (VI).
 8. The composition according toany of claims 1, 2, 6 or 7 wherein the composition after the combinationis adjusted to have a pH of 6 to
 12. 9. The composition according toclaim 1 or 2 wherein in the composition after the combination, based onits gross weight, 5 to 50 weight % of components (IV) and (II) and 0.1to 5 weight % of component (III) are contained.
 10. The compositionaccording to claim 6 or 7 wherein in the composition after thecombination, based on its gross weight, 5 to 50 weight % of components(IV) and (II), 0.1 to 5 weight % of component (III) and 0.01 to 5 weight% of component (VI) are contained.
 11. The composition according toclaim 1 or 2 wherein in the composition after the combination, based onits gross weight, 5 to 50 weight % of components (IV) and (II) and 0.1to 5 weight % of component (III) are contained, and the weight ratio ofcomponent (IV)/component (II) is 4/6 to 10/0.
 12. The compositionaccording to claim 6 or 7 wherein in the composition after thecombination, based on its gross weight, 5 to 50 weight % of components(IV) and (II), 0.1 to 5 weight % of component (III) and 0.01 to 5 weight% of component (VI) are contained, and the weight ratio of component(IV)/component (II) is 4/6 to 10/0.
 13. The composition according to anyof claims 1, 2, 6 or 7 wherein in the composition after the combination,based on its gross weight, the content of monohydric alcohols having 2to 5 carbon atoms is 3 weight % or less.
 14. The composition accordingto any of claims 1, 2, 6 or 7 wherein component (II) contains at leastone of surface active agents selected from the group consisting ofimidazolinium betaine-type amphoteric surface active agents,amidobetaine-type amphoteric surface active agents,amidosulfobetaine-type amphoteric surface active agents, betaine-typeamphoteric surface active agents, sulfobetaine-type amphoteric surfaceactive agents and tertiary amine oxide-type semipolar surface activeagents.
 15. The composition according to any of claims 1, 2, 6 or 7wherein component (II) is a mixture of at least one of imidazoliniumbetaine-type amphoteric surface active agents with at least one memberselected from the group consisting of amidobetaine-type amphotericsurface active agents, amidosulfobetaine-type amphoteric surface activeagents, betaine-type amphoteric surface active agents, sulfobetaine-typeamphoteric surface active agents and tertiary amine oxide-type semipolarsurface active agents.
 16. The composition according to any of claims 1,2, 6 or 7 wherein component (III) contains one or more of higher fattyacids composed of a straight-chain or branched chain, saturated orunsaturated hydrocarbon having 7 to 25 carbon atoms and optionallyhaving a hydroxyl group.
 17. The composition according to any of claims1, 2, 6 or 7 wherein component (IV) contains one or more of surfaceactive agents selected from the group consisting of polyoxyalkylenealkyl ether sulfate salts, alkyl ether sulfate salts, α-olefinsulfonatesalts and alkyloylalkyltaurine salts.
 18. The composition according toany of claims 1, 2, 6 and 7 wherein component (IV) contains one or moreof surface active agents selected from the group consisting ofpolyoxyethylene alkyl ether sulfate salts and alkyl ether sulfate saltshaving an alkyl chain having any even number of 10 to 18 carbon atoms.19. The composition according to claim 6 or 7 wherein component (VI)contains one or more of polymers selected from the group consisting ofquaternary nitrogen-containing cellulose derivatives,diallyldimethylammonium salt-acrylamide copolymers andpoly(diallyldimethylammonium salt) derivatives.
 20. The compositionaccording to claim 1 or 2 wherein in the composition after thecombination, based on its gross weight, 5 to 50 weight % of components(IV) and (II) and 0.1 to 5 weight % of component (III) are contained,and the weight ratio of component (IV)/component (II) is 4/6 to 6/4, andthe pH is 8 to
 12. 21. The composition according to claim 6 or 7 whereinin the composition after the combination, based on its gross weight, 5to 50 weight % of components (IV) and (II), 0.1 to 5 weight % ofcomponent (III) and 0.01 to 5 weight % of component (VI) are contained,and the weight ratio of component (IV)/component (II) is 4/6 to 6/4, andthe pH is 8 to
 12. 22. The composition according to claim 1 or 2 whereinin the composition after the combination, based on its gross weight, 5to 50 weight % of components (IV) and (II) and 0.1 to 5 weight % ofcomponent (III) are contained, and the weight ratio of component(IV)/component (II) is 4/6 to 6/4, and the pH is 6 or more and under 8.23. The composition according to claim 6 or 7 wherein in the compositionafter the combination, based on its gross weight, 5 to 50 weight % ofcomponents (IV) and (II), 0.1 to 5 weight % of component (III) and 0.01to 5 weight % of component (VI) are contained, and the weight ratio ofcomponent (IV)/component (II) is 4/6 to 6/4, and the pH is 6 or more andunder
 8. 24. The composition according to any of claims 1, 2, 6 or 7wherein in the composition after the combination, the weight ratio ofcomponent (IV)/component (II) is 6/4 to 10/0, the pH is 6 to 12, andcomponent (IV) contains one or more of surface active agents selectedfrom the group consisting of polyoxyethylene alkyl ether sulfate saltsand alkyl ether sulfate salts having an alkyl chain having any evennumber of 10 to 18 carbon atoms.
 25. The composition according to any ofclaims 1, 2, 6 or 7 wherein the composition after the combination doesnot contain component (II), the pH is 6 to 12, and component (IV)contains one or more of surface active agents selected from the groupconsisting of polyoxyethylene alkyl ether sulfate salts and alkyl ethersulfate salts having an alkyl chain having any even number of 10 to 18carbon atoms.
 26. The composition according to any of claims 1, 2, 6 or7 wherein the viscosity of the composition after the combination is 500cps or more at 30° C.